New mono- and bidentate P-ligands using one-pot click-chemistry: synthesis and application in Rh-catalyzed hydroformylation

Accepted Manuscript New Mono- and Bidentate P-Ligands Using One-pot Click-Chemistry: Synthesis and Application in Rh-Catalyzed Hydroformylation Natalia V. Dubrovina, Lutz Domke, Ivan A. Shuklov, Anke Spannenberg, Robert Franke, Alexander Villinger, Armin Börner PII:

S0040-4020(13)01189-7

DOI:

10.1016/j.tet.2013.07.070

Reference:

TET 24652

To appear in:

Tetrahedron

Received Date: 5 June 2013 Revised Date:

17 July 2013

Accepted Date: 18 July 2013

Please cite this article as: Dubrovina NV, Domke L, Shuklov IA, Spannenberg A, Franke R, Villinger A, Börner A, New Mono- and Bidentate P-Ligands Using One-pot Click-Chemistry: Synthesis and Application in Rh-Catalyzed Hydroformylation, Tetrahedron (2013), doi: 10.1016/j.tet.2013.07.070. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.

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New Mono- and Bidentate P-Ligands Using One-pot Click-Chemistry: Synthesis and Application in Rh-Catalyzed Hydroformylation

Natalia V. Dubrovina*, Lutz Domke, Ivan A. Shuklov, Anke Spannenberg, Robert Franke, Alexander Villinger, Armin Börner* +

R2

R1-Br 2 steps

R1 N N N

R2 = H, PAr2 R3 = Ar,OAr

AC C

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OH

OPR23

SC

NaN3

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Tetrahedron j o u r n a l h o m e p a g e : w w w . e l s e vi e r . c o m

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New Mono- and Bidentate P-Ligands Using One-pot Click-Chemistry: Synthesis and Application in Rh-Catalyzed Hydroformylation

Natalia V. Dubrovinaa∗, Lutz Domkea, Ivan A. Shuklovb, Anke Spannenbergb, Robert Frankec, Alexander Villingera and Armin Börnera,b∗ a

Institut für Chemie der Universität Rostock, Albert-Einstein-St. 3a, 18059 Rostock, Germany. Leibniz-Institut für Katalyse an der Universität Rostock e.V., Albert-Einstein-St. 29a, 18059 Rostock, Germany. c Evonik Industries GmbH, Paul-Baumann-Str. 1, 45 772 Marl, Germany.

SC

b

ABSTRACT

Article history: Received Received in revised form Accepted Available online

Three families of new phosphorus ligands have been prepared using the click-chemistry approach proceeding in only two steps and without intermediate P-protection. The methodology allows the high yield production of mono- and bidentate P-ligands, bearing at least one P-O bond. The ligands were tested in the Rh-catalyzed hydroformylation of 1-octene.

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ARTICLE INFO

2009 Elsevier Ltd. All rights reserved.

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Keywords: click chemistry cycloaddition phosphorus ligands multicomponent reactions hydroformylation

——— ∗ Corresponding author. Tel.: +49 381 498 6439; e-mail: [email protected] ∗ Corresponding author. Tel.: +49 381 1281 202; fax: +49 381 1281 51202; e-mail: [email protected]

ACCEPTED MANUSCRIPT Tetrahedron

Trivalent phosphorus compounds play a pivotal role as ancillary ligands in transition metal catalysis.1 Subtle differences in their electronic or steric properties may have a dramatic impact on the catalytic features of the resulting metal catalyst. Synthetic approaches which allow the preparation of large sets of strongly related ligands are therefore particularly interesting. Usually for the aim of variation a fixed organic scaffold is chosen and phosphorus units bearing varying substituents are linked to it. The modification of the scaffold would provide additional possibilities of variation provided that modular and easy to perform protocols are available. Of particular value in this connectivity is the concept of “click-chemistry” suggested by Sharpless and co-workers in 2001.2 The Cu(I)-catalyzed addition of organic azides to terminal acetylenes (CuAAC reaction) leading to 1,4-disubstituted 1,2,3triazoles is one of the most representative examples.3 Moreover, the reaction is nearly perfect in terms of atom economy and selectivity. It gives high yields and can produce compounds in a large diversity within a short time period. Therefore, it is not astonishing that for the purpose of ligand synthesis click chemistry has been already applied.

Interestingly only a very few P-O-ligands have been synthesized by this methodology. Thus, Zhang and Takacs prepared six diphosphites used as macrocycle forming ligands in the Rhcatalyzed asymmetric hydrogenation.10,11 A main advantage, the introduction of the P-unit could be accomplished in the last step by simple esterification of the phenolic hydroxyl groups. Therefore in contrast to other venues a tedious Pprotection/deprotection procedure is not required. Moreover, for some catalytic applications ligands with strong π-accepting P-Ogroups are more efficient than phosphines. A typical example concerns the Rh-catalyzed hydroformylation, where in particular phosphites are first choice as ligands due to the strong πaccepting properties.12 As a part of our ongoing studies concerned with the synthesis of chiral13 and achiral phosphorus ligands,14 herein we will show, that click-chemistry can be used for the preparation of numerous electron deficient ligands bearing at least one P-O bond, namely phosphinites and phosphites. A common feature of our protocol consists in the assembling of hydroxymethyl substituted 1,2,3triazole derivatives by a simple Cu(I) catalyzed one-pot reaction avoiding any organic azide in the first step followed by a phosphorylation reaction in the second, final step. Besides monodentate ligands of type A also bidentate hybrid ligands of type B ligands can be derived from this approach. Quasisymmetric bidentate ligands with the same P-units (C) have been produced by a related strategy.

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Thus, Zhang assembled ca. 10 phosphine ligands abbreviated as Clickphos on a 1,2,3-triazole backbone for Pd-catalyzed amination or Suzuki-Miyaura coupling reaction (Figure 1).4 The P-unit was connected to the heterocycle in the last step of the synthetic sequence.

dialkylphosphines also other potentially ligating groups, like 2pyridyl or alkylthio could be linked to the triazole. Kann and coworkers employed click chemistry for the preparation of a library of more than 20 P-chirogenic BH3 protected mono-phosphines.8 Matano and colleagues synthesized three α-(1-aryl-1,2,3-triazole4-yl)phospholes and used them in a study of the optical properties of corresponding Pd and Pt complexes.9 Phospholes were synthesized via their corresponding phosphine oxides, this approach required final deoxygenation with HSiCl3.

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1. Introduction

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2

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Figure 1. Phosphorus compounds useful for the application as ligands produced by click-chemistry.

Later on, Fukuzawa and co-workers prepared the first bidentate diphosphine ligands, called ClickFerrophos, by a similar pathway.5 In contrast for the synthesis of Clickphine ligands, Reek and van Maarseveen subjected propinyldiphenylphosphine to the cyclization reaction.6 This approach required the protection of the trivalent phosphorus as BH3 adduct. Both phosphine groups were incorporated in the last step. Due to the different reactivity of ferrocenyl and triazole unit even the introduction of two different PAr2 groups became possible. The two ligands derived were tested for asymmetric hydrogenation and allylic substitution, respectively. Pincer-ligands for the Heck reaction were constructed by Gandelman’s group by reaction of phosphinylmethyl azides with propinylphosphines.7 Also in this strategy the protection of the phosphine groups by BH3 or as phosphine oxide, respectively, was indispensable in each case. By extension of this methodology besides diaryl- or

To show the usefulness of the new ligands they were investigated in preliminary trials in the Rh-catalyzed hydroformylation of 1octene. 2. Results and Discussion Up to now, most P-ligands prepared by click-chemistry were assembled starting with organic azides. The latter are sometimes difficult to handle in particular when low weight organic azides have to be used. Therefore, we tried an alternative and safer approach. Commercially available and cheap propargyl alcohol was used as starting material. The in situ Cu(I)-catalyzed reaction was performed by a modification of the approach of Fokin and co-workers.15 Sodium azide and the corresponding alkyl bromides were reacted in the presence of copper(II) to give the corresponding organic azides, which in turn reacted without isolation with propargylic alcohol to afford 4-hydroxymethyl substituted 1,2,3-triazoles 1a-f in good yields (Table 1). It is noteworthy, that under these smooth conditions also a 1,2,3-triazole bearing in 1-position a non-benzylic sterically demanding substituent, such as 1cyclohexyl-4-(diphenylphosphinoxymethyl)-1H-1,2,3-triazole

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Table 1. Copper-catalyzed synthesis of 4-hydroxymethyl substituted 1,2,3-triazoles

Table 2. Synthesis of monodentate P-ligands 2a-h.

R1

(OR3)2

Yield

2a

Bn

-

98

2b

4-Me-C6H4CH2

-

98

2c

4-F-C6H4CH2

-

99

2d

4-CF3-C6H4CH2

-

>99

-

>99

-

>99

Product

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(1f) could be prepared although the product could be isolated only in a moderate yield. Alcohols 1a-f were characterized by 1H, 13 C and – in the case of 1d,e - also using 19F NMR spectroscopy as well as mass spectrometry. All products are crystalline and were purified in a single crystallization step.

R1

Yield [%]

2e

3-F-C6H4CH2

1a

Bn

73

2f

cHex

1b

4-Me-C6H4CH2

93

2g

4-Me-C6H4CH2

(R)-Binaphthoxy

93

2h

4-F-C6H4CH2

(R)-Binaphthoxy

96

4-F-C6H4CH2

88

4-CF3-C6H4CH2

94

1e

3-F-C6H4CH2

82

1f

cHex

39

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1c 1d

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Product

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The structure of 1,2,3-triazole 1f was additionally analyzed by X-ray structural analysis. Suitable crystals were obtained by crystallization from dichloromethane/n-heptane. The solid-state structure of 1-cyclohexyl-4-(hydroxymethylmethyl)-1H-1,2,3triazole (1f) is depicted in Figure 2 and confirms the expected molecular structure.

2.2 Synthesis of bidentate hybrid ligands (Type B)

The success of our methodology for the synthesis of monodentate P-ligands prompted us also to test it in the synthesis of bidentate P-ligands via lithiation of the triazole unit as illustrated in Table 3. In our first trials, triazoles 1a-c were treated with two equivalents of n-BuLi. We were pleased to see that besides the hydroxyl group also the proton of the 1,2,3triazole is sufficiently acidic and can be removed. Upon reaction with iodine and subsequent addition of water iodides 3a,b could be isolated in good yields (up to 83 %) as crystalline materials by a single recrystallization from ethyl acetate.

Table 3. Synthesis of bidentate ligands 5a-d via dilithiation of 1,2,3-triazoles 1a-c. OH

Figure 2. ORTEP diagram of triazole 1f, top view. The thermal ellipsoids correspond to 30 % probability

EP

R1 N N N

AC C

3a,b X 1. 2 eq. n-BuLi 2. 2 eq. Ph2PCl

2 eq. n-BuLi

In the next step 4-hydroxymethyl-1,2,3-triazoles 1a-f were converted selectively into the corresponding phosphinites 2a-f. Lithiation of the alcohols using one equivalent of n-BuLi, followed by addition of one equivalent ClPPh2 gave the desired phosphinites in nearly quantitative yields (Table 2). Moreover, we found that (R)-binaphthophosphochloridite which yields in a prior esterification of (R)-binaphthol with PCl3 also reacts with

OLi

Li

2 eq R22PCl R1 N N N

PR22

OPR22

R1 N N N 5a-d

4a-c

Product

OH

I R1 N N N

1a-c

2.1 Synthesis of monodentate phosphinite and phosphite ligands (Type A)

the intermediate Li-alcoholates to give phosphites 2g,h.

1. 2 eq n-BuLi 2. I2/H2O

R1

R2

Yield

5a

Bn

Ph

98

5b

4-Me-C6H4CH2

Ph

98

5c

4-Me-C6H4CH2

3,5-(CF3)2-C6H4CH2

95

5d

4-F-C6H4CH2

Ph

97

Crystals of iodide 3b were analyzed by X-ray crystallography which confirmed the expected structure (Figure 3).

ACCEPTED MANUSCRIPT Tetrahedron

As an alternative synthetic approach we envisaged the direct phosphorylation of the dilithium salts 4a-c by treatment with two equivalents of Ar2PCl which afforded the desired phosphinophosphinites 5a-d in nearly quantitative yields (Table 3). Unfortunately, the reaction with an excess of (R)binaphthophosphochloridite was not successful, probably the linkage of this phosphonite group to the triazole moiety is not favored due to steric hindrance.

Product

R

Yield [%]

8a

Ph

8b

(R)-Binaphthoxy

97

8c

3,5-(CF3)2-C6H4CH2

96

99

The possibility of ligands of type 8 to chelate to metals was again proven by formation of the corresponding Pt-complexes. In the 31 P NMR spectra of PtCl2(8a or 8b) the cis-chelation was confirmed by two doublets of pseudotriplets at δ 87.06 (dd, 1J(P-Pt) = 4187.9, 2J(P-P) = 7.4 Hz) and δ 88.6 (dd, 1J(P-Pt) = 4216.9 Hz, 2J(P31 P NMR of the BINOL-based P) = 7.4 Hz), respectively. The complex Pt(8b)Cl2 showed two sets of resonances at δ 88.7 (br, d, 1J(P-Pt) = 5562 Hz, 2J(PP) = 24 Hz) and at δ 93.7 (d, 1J(P-Pt) = 5542 Hz, 2J(P-P) = 24 Hz).

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Figure 3. ORTEP diagram of iodo-triazole 3b top view. The thermal ellipsoids correspond to 30 % probability

Table 4. Synthesis of bidentate diphosphite ligands from 2butyne-1,4-diol (6).

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In the next approach, we tried to synthesize bidentate P,Pligands by treatment of iodide 3a,b by double phosphorylation with chlorophosphines. Unfortunately, all attempts to react the iodides with two equivalents of n-BuLi and subsequent C-Pcoupling with Ph2PCl failed. Prolongation of the reaction time and enhancement of the temperature gave an inseparable mixture of products.

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In order to prove that these phosphine-phosphinites can act as bidentate ligands, we prepared corresponding Pt and Pd complexes. When 5a was reacted with [PtCl2(COD)] or Pd(MeCN)2Cl2 analytically pure Pt(5a)Cl2 and Pd(5a)Cl2, respectively, were obtained. In the 31P NMR spectrum the Ptcomplex showed the typical pattern of a complex with a ciscoordinated ligand.16 Two doublets at δ -12.4 (br, d, 1J(P-Pt) = 3722 Hz, 2J(P-P) = 15 Hz) and at δ 90.6 (d, 1J(P-Pt) = 3864 Hz, 2J(P-P) = 15 Hz) were observed. Pd(5a)Cl2 was likewise characterized by two doublets at δ 1.5 (2J(P-P) = 18 Hz) and at δ 120.2 (2J(P-P) = 17 Hz). The analogous complexes Pt(5b,c)Cl2 and Pd(5b,c)Cl2 displayed a similar spectroscopic behavior.

2.3 Synthesis of bidentate diphosphite ligands (Type C)

AC C

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Our pathway for the synthesis of quasi-symmetric diphosphite ligands of type C is shown in Table 4. It is based on the cyclization of 2-butyne-1,4-diol. Unfortunately, under the smooth reaction conditions described above only 5 % of the desired diol was formed. More successful revealed the synthesis via a slightly modified route recommended by Tikhonova17 and Liu,18 which proceeds by heating of benzyl bromide with a mixture of but-2yne-1,4-diol and sodium azide in DMF at 130 °C for 13 h. 1Benzyl-4,5-di(hydroxymethyl)-1H-[1,2,3]triazole (7) which was only scarcely characterized in the literature was obtained in a yield of 55 %. Subsequent lithiation of 1,4-diol 7 with two equivalents of n-BuLi, followed by phosphorylation with ClPAr2 provided diphosphinites 8a,c (Table 4). Likewise the esterification with (R)-binaphthophosphochloridite proceeded successfully and gave the diphosphite 8b in nearly quantitative yield.

2.4 Application of triazole based phosphorus ligands in the Rh-catalyzed hydroformylation

Rhodium-catalyzed hydroformylation of non-branched olefins is one of the most important processes in industrial homogeneous catalysis.12 Therefore, the hydroformylation of 1-octene was chosen to test the activities and regioselectivities induced by the new phosphorus compounds as ligands in corresponding Rh catalysts. The required precatalysts were generated in situ by reaction of [Rh(acac)(COD)] with 5 equivalent of the monodentate or 2 equivalent of the bidentate phosphorus ligands. The reactions were carried out at a temperature of 100 °C under 20 or 50 bar of syngas pressure (CO/H2 ratio 1:1). As solvent toluene was used. Results are detailed in Table 5. Monodentate phosphinite and phosphite 2a-h have shown good activity and moderate till good selectivities compared to classical monodentate ligands.12,21 In almost all cases rather complete conversion was noted within 4 h. n-Regioselectivities induced by diphenylphosphinites 2a-f are moderate and within a narrow range. Decrease of the syngas pressure from 50 to 20 bars enhanced the n-regioselectivity without affecting the rate (Table 4, runs 1,3). A further improvement of this parameter up to 75 % could be achieved by application of the bulky BINOL-derived phosphites 2g and 2h (Table 4, runs 7,8). Bidentate hybrid ligands 5a-d also induced only moderate regioselectivity (Runs 9-12). The best value gives the catalyst derived from 5c bearing electron-withdrawing P-Ar units (Run 12). In comparison to the literature,12,22 bidentate dipphosphite ligands 8a-c exhibited good n-selectivities (up to 87 %) and good activity. Interestingly among the quasi-symmetric ligands 8a-c tested the diphenylphosphine based ligand 8a induced the highest nregioselectivity (Run 13), whereas incorporation of four electronwithdrawing CF3-groups in the phenyl rings (8c) caused a drastic

ACCEPTED MANUSCRIPT 5 lowering of this value (Run 15). The diphosphite 8b forms also a very active, but only moderately regioselective catalyst (Run 14). Table 5. Rhodium-catalyzed hydroformylation of 1-octenea

Ligand

p [bar]

Conversionb

n-Regioselectivityc

1

2a

20

96

67

2

2b

50

94

58

3

2c

20

96

66

4

2d

50

98

59

5

2e

50

99

56

6

2f

50

98

58

7

2g

20

94

75

8

2h

50

99

71

9

2h

20

99

73

10

5ad

50

94

68

d

50

94

62

d

50

88

76

d

50

94

54

d

50

74

87

d

50

97

61

d

50

95

53

12 13 14 15 16

5b 5c

5d 8a

8b 8c

a

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Conditions: [Rh(acac)(cod)], Rh:L:olefin = 1:5:2000, 100 ppm [Rh], toluene, 4 h; b Determined by GC, cratio of n-nonanal relative to the overall yield of aldehydes; dRh:L = 1:2.

4.2. Hydroformylations

3. Summary and Conclusion

Hydroformylation experiments were carried out in 25 mL or 200 mL autoclaves at 100-120 °C and 20 or 50 bar syngas (99.997%; CO/H2 = 1:1) for 4 h. The autoclave was purged and filled with syngas before the precatalyst solution and olefin was introduced into the reactor. After 4 h the autoclave was cooled to room temperature and then the pressure was released in a wellventilated hood. The reactions mixture was analyzed by gas chromatography on a HP 5890 Series II or Agilent 7890 A with a 30 m HP5 column to determine conversion and regioselectivity.

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11

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Run

Solvents were dried and freshly distilled under argon before use. Thin-layer chromatography was performed on pre-coated TLC plates (silica gel 60 F254, Merck). Flash chromatography was carried out with silica gel 60 (230–400 mesh ASTM). PCl3 and NEt3 were distilled immediately before use. NMR 1H (250.1, 300.1 and 500.1 MHz), 31P (121.5 MHz), 13C (62.9, 75.5 and 125.7 MHz) and 19F (282 MHz) spectra were recorded on a Bruker AC 250, ARX 300 and AVANCE 500 respectively. Chemical shifts δ are quoted in parts per million (ppm) and are referred to the resonance of tetramethylsilane. 31P NMR chemical shifts were referenced externally to 85% H3PO4 (δ 0.0). Coupling constants J are given in Hz. EI mass spectra were measured on a Finnigan MAT 95-XP mass spectrometer (Thermo Electron Corporation). HRMS was performed on MAT 95-XP (EI) and Agilent 6210 Time-of-Flight LC/MS (ESI). GC-MS was performed on Agilent 5973 chromatograph mass selective detector. GC was performed on Agilent 7890 A chromatograph with a 30 m HP5 column.

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Three sets of new closely related mono- und bidentate ligands based on 1,2,3-triazole backbone have been prepared using click-chemistry approach within two steps. The new electron deficient P-ligands bearing at least one P-O bond were prepared from easily available starting materials. Preparation and isolation of dangerous explosive organic azides could be avoided in this way. Moreover, a new methodology for the one-pot synthesis of bidentate ligands via direct dilithiation and subsequent phosphorylation was developed. In order to prove the complexation behavior of new ligands corresponding Pt and Pd complexes were synthesized and characterized. The usefulness of this type of ligands was demonstrated in the Rh-catalyzed hydroformylation of 1-octene. In most cases high conversions and good n-regioselectivities of up to 87 % were achieved.

4. Experimental section 4.1. General methods Unless otherwise stated, all reactions were carried out under a dry argon atmosphere using standard Schlenk-line techniques. All reagents, unless otherwise mentioned, were purchased from commercial sources and used without additional purification.

4.3. X-ray Crystallographic Study of 1f and 3b

Data were collected on a Bruker Kappa Apex II diffractometer using graphite monochromated Mo Kα radiation (λ = 0.71073). The structures were solved by direct methods (SHELXS-97)19 and refined by full-matrix least-squares procedures (SHELXL-97). CCDC-882434 (for 1f) and CCDC-884751 (for 3b) contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac.uk/data_request/cif.

4. 3. 1. C r y st al da t a f or 1- c yc l o h ex y l- 4(h y dr o xy m et h yl )- 1 H - 1, 2, 3- tr i az o le (1 f ): C9H15N3O, Mr = 181.24, monoclinic, space group P21/c, a = 14.2822(4), b = 8.3517(2), c = 8.0670(3) Å, α = 90.00, β = 94.301(2), γ = 90.00°, V = 959.53(5) Å3, Z = 4, ρcalcd. = 1.255 g cm–3, µ = 0.085 mm–1, T = 173(2) K, 2795 independent reflections, of which 1905 were observed [I>2σ(I)], 122 parameters, final R values [I>2σ(I)]: R1 = 0.0428, wR2 = 0.1002, final R values (all data): R1 = 0.0758, wR2 = 0.1094, largest diff. peak and hole 0.28/-0.19 e·Å–3. 4. 3. 2. C r y st a l da t a f or 1- (4- m e t h ox y be n z y l )- 4(h y dr o xy m et h yl )- 5- i o d o- 1 H- 1, 2, 3- tr i az ol e (3 b ) C11H12IN3O, Mr = 329.14, orthorhombic, space group P212121, a = 5.8628(1), b = 7.5482(1), c = 26.7283(6) Å, V = 1182.82(4) Å3, Z = 4, ρcalcd = 1.848 g ⋅ cm-3, µ = 2.69 mm-1, T = 150(2) K, 2968 independent reflections, of which 2948 were observed [I > 2σ(I)], 147 parameters, final R values [I > 2σ(I)]: R1 = 0.0214, wR2 = 0.0528, final R values (all data): R1 = 0.0217, wR2 = 0.0529, largest diff. peak and hole 0.62 and -0.76 e⋅Å-3.

ACCEPTED MANUSCRIPT Tetrahedron

A mixture of 1-propinol (2.90 g, 0.05 mol), aryl- or alkylbromide (0.05 mol), L-proline (1.15 g, 0.01 mmol), sodium azide (3.90 g, 0.06 mol), sodium carbonate (1.05 g, 0.01 mol) and sodium ascorbate (2.00 g, 0.01 mol) was stirred in 90 ml DMSO and H2O 10 ml. CuSO4*5H2O (2.90 g, 0.005 mol) was added (attention, self-warming). Then the reaction was run at 65 °C for 18 h. The mixture was poured into ice and the product was extracted with CH2Cl2 (4x150 mL). The combined organic phases were washed with 5 % ammonia solution (2x150 mL) to remove traces of azide. The organic layer was washed with brine (150 mL) and dried over Na2SO4. The organic solvent was removed under reduced pressure to give the crystalline product. Additional purification could be achieved via crystallization from ethyl acetate.

4. 4 . 1. 1 -B e n zy l- 4- (h y dr o x y m et h yl )- 1 H- 1, 2, 3tr i az ol e (1 a ) Colorless crystals, yield 73 %, mp 77-78 °C. For NMR spectra see Ref.20

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4. 4 . 3. 1 - (4 - F l u or o be nz yl )- 4- (h y d r ox y m e t h yl )- 1 H 1, 2 , 3- tr ia z ole (1 c ) Colorless crystals, yield 88 % mp 67-68 °C. For NMR spectra see Ref.20

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4. 4 . 4. 1 - (4 -T r ifl u or o m e t hy l b e n z y l )- 4(h y d r o x y m e t h yl )- 1 H - 1, 2, 3- tr i az o le (1 d ) Colorless crystals, yield 94 % mp 99.5-100.5 °C. 1H NMR (300 MHz, CDCl3): δ = 3.47 (br, 1H, OH), 4.75 (s, 2H, CH2OH), 5.56 (s, 2H, CH2), 7.35 (d, 3J(H-H) = 8.12 Hz, 2H, CHAr), 7.5 (s, 1H, Htrz) 7.61 (d, 3J(H-H) = 7.93 Hz, 2H, CHAr) ppm. 13C NMR (63 MHz, CDCl3): δ = 53.5 (CH2), 56.3 (CH2 OH), 121.8 (CHtrz), 123.7 (q, 1J(C-F) = 272.4 Hz, CF3), 126.1 (q, 3J(C-F) = 3.6 Hz, CHAr), 128.2 (CHAr), 131.1 (q, 2J = 32.5 Hz, CCF3), 138.4 (CAr), 148.4 (Ctrz) ppm. 19F NMR (282 MHz, CDCl3): δ = -62.8 ppm. MS (EI, 70 eV): m/z (%) = 257 (2) [M]+, 159 (100), 109 (28). HRMS (ESI) for C11H11F3N3O found: 258.08487 [M+H]+, calcd. 258.08511 [M+H]+. Calcd for C11H10F3N3O (257.21): C, 51.37; H, 3.92; N, 16.34. Found: C, 51.70; H, 3.88; N, 16.29.

AC C

4. 4. 6. 1- C y cl o he x y l- 4- (h y dr o x y m e t h yl )-1 H - 1 , 2, 3 tr i az o l e (1 f ) Colorless crystals, yield 82 % mp 93.5-84.5 °C. 1H NMR (300 MHz, CDCl3): δ = 1.19-1.33 (m, 1H, CH2), 1.37-1.52 (m, 2H, CH2), 1.66-1.78 (m, 3H, CH2CH2), 1.88-1.94 (m, 2H, CH2), 2.162.21 (m, 2H, CH2), 3.34 (brs, 1H, OH), 4.36-4.47 (m, 1H, CH), 4.76 (s, 2H, CH2), 7.54 (s, 1H, Htrz) ppm. 13C NMR (63 MHz, CDCl3): δ = 25.1, 33.5 (CH2), 56.3 (CH2OH), 60.1 (CH), 119.4 (CHtrz), 147.2 (Ctrz) ppm. MS (EI, 70 eV): m/z (%) = 181 (21) [M]+, 83 (29), 82 (19), 55 (100), 41 (49), 39 (28). HRMS (ESI) for C9H16N3O found: 182.12879 [M+H]+, calcd. 182.12873 [M+H]+. Calcd. for C9H15N3O (181.23): C, 59.64; H, 8.34; N, 23.19. Found: C, 60.08; H, 8.21; N, 22.89.

4.5. Synthesis procedure

of

monodentate

ligands

2a-f.

General

A solution of 1.6 M n-BuLi (0.94 ml, 0.0015 mol) was added to a solution of the triazole (0.0015 mol) in THF (20 mL) at -78 °C. The resulting mixture was allowed to warm up to ambient temperature and stirred for 30 min. Afterwards, the reaction mixture was added slowly to a solution of diphenylchlorophosphine (0.33 g, 0.0015 mol) in 5 ml THF at 0 °C. The mixture was warmed to ambient temperature and stirred overnight. Then the solvent was evaporated under reduced pressure. The residue was transferred into toluene (10 mL), and the solution was filtered to give the pure product in nearly quantitative yield.

M AN U

4. 4 . 2. 1 - (4 -M et hy l be nz yl )- 4- (h y d r ox y m e t h yl )- 1 H 1, 2 , 3- tr ia z ole (1 b ) Colorless crystals, yield 93 %, mp 91.5-92.5 °C. For NMR spectra see Ref.20

[M+H]+. Anal. Calcd. for C10H10FN3O (207.20): C, 57.97; H, 4.86; N, 20.28. Found: C, 58.23; H, 4.90; N, 19.77.

RI PT

4.4. Synthesis of 1,2,3-triazole 1a-f. General procedure.

SC

6

4. 4 . 5. 1 - (3 - F l u or o be nz yl )- 4- (h y d r ox y m e t h yl )- 1 H 1, 2 , 3- tr ia z ole (1 e ) Colorless crystals, yield 82 % mp 70.5-71.5 °C . 1H NMR (300 MHz, CDCl3): δ = 3.24 (brs, 1H, OH), 4.69 (s, 2H, CH2OH), 5.43 (s, 2H, CH2), 6.85-6.90 (m, 1H, CHAr), 6.93-7.00 (m, 2H, CHAr ), 7.23-7.30 (m, 1H, CHAr ), 7.42 (s, 1H, Htrz) ppm. 13C NMR (75 Hz, CDCl3): δ = 53.4 (CH2), 56.2 (CH2OH), 115.0 (d, 2J = 22.0 Hz, CHAr), 115.7 (d, 2J = 20.9 Hz, CHAr), 121.8 (CHtrz), 123.5 (d, 4 J = 3.3 Hz, CHAr), 130.7 (d, 3J = 8.3 Hz, CHAr), 136.8 (d, 3J = 7.7 Hz, CAr), 148.3 (Ctrz), 162.9 (d, 1J = 247.6 Hz, CF) ppm. 19F NMR (282 MHz, CDCl3): δ = -111.6 ppm. MS (EI, 70 eV): m/z (%) = 207 (2) [M]+, 161 (12), 109 (100), 83 (19). HRMS (ESI) for C10H11FN3O found: 208.08807 [M+H]+, calcd. 208.08842

4. 5. 1. 1- B e nz y l - 4- (d i p he n yl p h o s p hi n ox y m et h y l )- 1 H 1, 2, 3- tr ia z o le (2 a ) Colorless powder, yield 0.547 g (97.7 %). 1H NMR (300 MHz, CDCl3): δ = 4.93 (d, 2H, 3J(H-P) = 10.4 Hz, CH2O), 5.38 (s, 2H, CH2), 7.10-7.14 (m, 2H, CHAr), 7.20-7.29 (m, 10 H, CHAr and Htrz), 7.32-7.40 (m, 4H, CHAr) ppm. 13C NMR (75.5 MHz, CDCl3): δ = 54.1 (CH2), 63.5 (d, 2J(C-P) = 21 Hz, CH2O), 122.4 (C5trz), 128.0 (CAr), 128.3 (Cm-P, d, 3J(C-P) = 6.8 Hz, CAr), 128.7 (Cp-P), 129.1 (CAr), 129.5 (CAr), 130.6 (Co-P, d, 2J(C-P) = 22 Hz, CAr), 134.5 (q, CAr), 141.2 (q, CP, d, 1J(C-P) = 18 Hz, CAr), 146.2 (q, C4trz, d, 3J(C-P) = 8 Hz). 31P NMR (121.5 MHz, CDCl3): δ 116.0 ppm. MS (EI, 70 eV): m/z (%) = 373 (38) [M]+, 372 (35) [M-1]+, 249 (82), 201 (100) [Ph2PO]+, 91 (58). HRMS (ESI) for C22H21N3OP found: 374.1422 [M+H] +, calcd. 374.1417 [M+H]+. HRMS (ESI) for C22H20N3NaOP found: 396.1242 [M+Na]+; calcd. 396.1236 [M+Na] +.

4. 5. 2. 1- (4 - M et h y l be nz y l )- 4(d i p he n yl p h os p h i n ox y m et h y l)- 1 H- 1, 2, 3- tr i az ol e (2 b ) Colorless powder, yield 0.571 g (98.3 %). 1H NMR (300 MHz, CDCl3): δ = 2.27 (3H, s, CH3), 4.91 (2H, d, 3J(H-P) = 10.3 Hz, CH2O), 5.33 (2H, s, CH2), 6.99-7.10 (m, 4H, CHAr), 7.207.26 (m, 7 H, CHAr and Htrz), 7.32-7.40 (m, 4H, CHAr) ppm. 13C NMR (62.9 MHz, CDCl3): δ = 21.2 (CH3), 53.8 (CH2), 63.4 (d, 2 J(C-P) = 21 Hz, CH2O), 122.3 (C5trz), 128.1 (CAr), 128.3 (Cm-P, d, 3 J(C-P) = 7 Hz, CAr), 129.4 (Cp-P), 129.7 (CAr), 130.5 (Co-P, d, 2J(C-P) = 22 Hz, CAr), 131.5 (q, CAr), 138.6 (q, CCH3), 141.2 (q, CP, d, 1 J(C,P) = 18 Hz, CAr), 146.1 (q, C4trz, d, 3J = 8 Hz) ppm. 31P NMR (121.5 Hz, CDCl3): δ = 115.9 ppm. MS (EI, 70 eV): m/z (%) = 387 (9) [M]+, 386 (4) [M-H]+, 263 (63), 202 (44), 201 (96), 105

ACCEPTED MANUSCRIPT 7

4.6. Synthesis of monodentate ligands 2g-h. General procedure 1-Methylpyrrolidin-2-one (0.01 g, 0.1 mmol) was added to a stirred mixture of (R)-binaphthol (0.429 g, 0.0015 mol) and PCl3 (4 mL). The mixture was refluxed for 20 min until it became completely homogeneous. Subsequently all volatiles were removed under vacuum. Toluene (5 mL) was added and the solvent was evaporated on a vacuum line to remove traces of PCl3. The product binaphtholchlorophosphite was dried under vacuum for 1 h. In a separate vessel a solution of 1.6 M n-BuLi (0.94 mL, 0.0015 mol) was added to a solution of the relevant triazole (0.0015 mol) in THF (20 mL) at -78 °C. The resulting orange mixture was allowed to warm up to ambient temperature and stirred for 30 min. This mixture was added slowly to a stirred solution of binaphtholchlorophosphite in THF (5 mL) at 0 °C. The reaction mixture was stirred overnight at room temperature. The solvent was evaporated under reduced pressure. The residue was transferred into toluene (10 mL) and the solution was filtered off to give the pure product as a lightly yellow foam.

TE D

M AN U

4. 5 . 4. 1 - (4 -T r ifl u or o m e t hy l b e n z y l )- 4(d i p he n yl p h os p hi n ox y m et hy l)- 1 H- 1, 2, 3- tr i az ol e (2 d ) Colorless powder, yield 0.658 g (99.5 %). 1H NMR (300 MHz, CDCl3): δ = 4.96 (dd, J = 0.6 Hz, 3J(P-H) = 10.6 Hz, 2H, CH2OP), 5.45 (s, 2H, CH2), 7.19 (m, 1H, CHAr), 7.22-7.25 (m, 7H, CHAr), 7.28 (s, 1H, Htrz), 7.34-7.40 (m, 4H, CHAr) 7.51-7.54 (m, 2H, CHAr) ppm. 13C NMR (75 Hz, CDCl3): δ = 53.2 (CH2), 63.3 (d, 3J(C-P) = 20.9 Hz, CH2OP), 122.5 (CHtrz), 123.8 (q, 1J(C-F) = 272.3 Hz, CF3), 125.9 (q, 3J(C-F) = 3.9 Hz, CHAr), 128.0 (CHAr), 128.2 (d, 3J(C-P) = 7.2 Hz, CHAr) 129.4 (CHAr), 130.4 (d, 2J(C-P) = 22.0 Hz, CHAr) 130.7 (q, 2J(C-F) = 32.5 Hz, CCF3), 138.5 (CAr), 141.1 (d, 1J(C-P) = 18.2 Hz, CAr), 146.4 (d, 3J(C-P) = 7.7 Hz, Ctrz) ppm. 31P NMR (121 MHz, CDCl3): δ = 116.2 ppm. 19F NMR (282 MHz, CDCl3): δ = -62.8 ppm. HRMS (ESI) for C23H20F3N3OP found: 442.12818 [M+H]+, calcd. 442.12906 [M+H]+.

RI PT

4. 5 . 3. 1 - (4 - F l u or o be nz yl )- 4(d i p he n yl p h os p hi n ox y m et hy l)- 1 H- 1, 2, 3- tr i az ol e (2 c) Colorless powder, yield 0.580 g (99 %). 1H NMR (300 MHz, CDCl3): δ = 4.93 (2H, d, 3J(H-P) = 10.5 Hz, CH2 O), 5.35 (2H, s, CH2), 6.92-7.00 (m, 2 H, CHAr), 7.07-7.14 (m, 2 H, CHAr), 7.21– 7.28 (m, 7 H, CHAr and Htrz), 7.32-7.41 (m, 4 H, CHAr) ppm. 13C NMR (75.5 MHz, CDCl3): δ 53.3 (CH2), 63.5 (d, 2J(C-P) = 21 Hz, CH2O), 116.1 (Co-F, d, 2J(C,F) = 22 Hz), 122.3 (C5trz), 128.3 (Cm-P, d, 3J(C-P) = 7 Hz), 129.5 (Cp-P), 129.9 (Cm-F, d, 3J(C,F) = 8.2 Hz), 130.4 (q, Cp-F), 130.5 (Co-P, d, 2J(C-P) = 22 Hz), 141.2 (q, CP, d, 1 J(C,P) = 18 Hz), 146.3 (q, C4trz, d, 3J(C,P) = 8 Hz), 162.9 (q, CF, d, 1 J(C,F) = 248 Hz) ppm. 31P NMR (121.5 Hz, CDCl3): δ = 115.9 ppm. 19F NMR (282 MHz, CDCl3): δ = -112.3 ppm. HRMS (ESI) for C22H20FN3OP found: 392.13313 [M+H]+, calcd. 392.132225 [M+H]+. HRMS (ESI) for C22H19FN3NaOP found 414.1153 [M+Na]+, calcd. 414.1142 [M+Na]+.

(m, 2H, CH2), 4.25-4.36 (m, 1H, CH), 4.95 (dd, J = 0.6 Hz , 3 JP-H = 10.4 Hz, 2H, CH2), 7.25 – 7.29 (m, 6H, CHAr), 7.31 (s, 1H, Htrz), 7.38-7.43 (m, 4H, CHAr) ppm. 13C NMR (75 MHz, CDCl3): δ = 25.1, 33.4 (CH2) 59.9 (CH), 63.6 (d, 2J = 20.9 Hz, CH2), 120.1 (CHtrz), 128.3 (d, 3J = 6.6 Hz, CHAr), 129.4 (CHAr), 130.5 (d, 2J = 21.5 Hz, CHAr), 141.3 (d, 1J = 17.6 Hz, CAr), 145.2 (d, 3J = 8.3 Hz, Ctrz) ppm. 31P NMR (121 MHz, CDCl3): δ = 115.7 ppm. HRMS (ESI) for C21H25N3OP found: 366.17313 [M+H]+, calcd. 366.17298 [M+H]+.

SC

(100). HRMS (ESI) for C23H23N3OP found: 388.15733 [M+H]+, calcd. 388.15719 [M+H]+. HRMS (ESI) for C23H22N3NaOP found: 426.13418 [M+Na]+, calcd. 426.1341 [M+Na]+.

AC C

EP

4. 5 . 5. 1 - (3 - F l u or o be nz yl )- 4(d i p he n yl p h os p hi n ox y m et hy l)- 1 H- 1, 2, 3- tr i az ol e (2 e ): Colorless solid, yield 0.584 g (99.4 %). 1H NMR (300 MHz, CDCl3): δ = 4.94 (dd, J = 0.6 Hz, 3J(P-H) = 10.6 Hz, 2H, CH2OP), 5.37 (s, 2H, CH2), 6.79-6.84 (m, 1H, CHAr), 6.88-6.91 (m, 1H, CHAr), 6.93-7.00 (m, 1H, CHAr), 7.23-7.26 (m, 8H, CHAr and Htrz), 7.35-7.40 (m, 4H, CHAr) ppm. 13C NMR (75 MHz, CDCl3): δ = 53.4 (d, 4J(C-F) = 2.2 Hz, CH2), 63.5 (d, 2J(C-P) = 21.5 Hz, CH2OP), 115.0 (d, 2J(C-F) = 22.6 Hz, CHAr), 115.8 (d, 2J(C-F) = 20.9 Hz, CHAr), 122.5 (CHtrz), 123,5 (d, 4JC-F = 2.8 Hz, CHAr), 128.3 (d, 3J(C-P) = 6.6 Hz, CHAr), 129.5 (CHAr), 130.6 (d, 2J(C-P) = 21.5 Hz, CHAr), 130.8 (CHAr) 136.9 (d, 3J(C-F) = 7.7 Hz, CAr), 141.2 (d, JC-P = 17.6 Hz, CAr), 146.4 (d, 3J(C-P) = 7.7 Hz, Ctrz), 163.0 (d, 1J(C31 F) = 247.6 Hz, CF) ppm. P NMR (121 MHz, CDCl3): δ = 116.3 ppm. 19F NMR (282 MHz, CDCl3): δ = -111.6 ppm. HRMS (ESI) for C22H20FN3OP [M+H]+ found: 392.13272 [M+H]+, calcd. 392.13225 [M+H]+.

4. 5 . 6. 1 - C y c l o he x y l- 4(d i p he n yl p h os p hi n ox y m et hy l)- 1 H- 1, 2, 3- tr i az ol e (2f ): Colorless solid, yield 0.544 g (99.3 %). 1H NMR (300 MHz, CDCl3): δ = 1.14-1.24 (m, 1H, CH2), 1.27-1.47 (m, 2H, CH2), 1.51-1.66 (m, 3H, CH2CH2), 1.78-1.85 (m, 2H, CH2), 2.03-2.09

4. 6. 1. 4- Di n a p ht h o [1 , 2- f: 2´ , 1´ d] [1, 3, 2, ] di o x a p h os p he p hi n- 4- y l o xy m et h yl- 1- (4 fl u or ob e nz y l )- 1 H- 1 , 2 , 3- t r ia z o le (2 g ) Colorless solid. Yield 0.752 g (96.3 %). 1H NMR (300 MHz, C6D6): δ = 4.76 (2H, d, 3J(H-P) = 1.2 Hz, CH2 O), 5.00-5.19 (2H, m, CH2), 6.67-7.75 (m, 17 H, CHAr and Htrz), ppm. 13C NMR (75.5 MHz, C6D6): δ 52.7 (CH2), 58.8 (d, 2J(C,P) = 4.5 Hz, CH2O), 115.3 (Co-F, d, 2J(C,F) = 22 Hz), 121.5 (d, J = 5.8 Hz, CAr), 122.0 (C5trz), 124.7 (d, J = 12 Hz, CAr), 126.2 (d, J = 3.2 Hz, CAr), 126.7 (d, J = 9.2 Hz, CAr), 128.2 (CAr), 129.4 (d, J = 8.2 Hz Cm-F, d, 3 J(C,F) = 8.2 Hz), 130.2 (d, Co-P, d, 2J(C-P) = 22 Hz), 130.8 (q, CAr), 131.4 (q, CAr), 132.6 (q, d, J = 22.9 Hz, CAr), 144.9 (q, d, J(CP) = 4.4 Hz, CAr), 148.0 (q, d, J(CP) = 2.2 Hz, CAr), 149.5 (q, d, J(CP) = 5.3 Hz, CAr), 163.0 (q, CF, d, 1J(C,F) = 246 Hz) ppm. 31P NMR (75.5 MHz, C6D6): δ = 151.9 ppm, 19F NMR (282.4 MHz, C6D6): δ = -113.2 ppm. MS (EI, 70 eV): m/z (%) = 521 (2) [M]+, 286 (53) [binaphthdioxy]+, 105 (100). HRMS (ESI) for C30H22FN3O3P found: 522.13841 [M+H]+, calcd. 522.13773 [M+H]+. HRMS (ESI) for C30H21FN3NaO3P found: 544.12062 [M+Na]+, calcd. 544.11968 [M+Na] +.

4. 6. 2. 4- Di n a p ht h o [1 , 2- f: 2´ , 1´ d] [1, 3, 2, ] di o x a p h os p he p hi n- 4- y l o xy m et h yl- 1- (4 m et h y l be n zy l )- 1 H- 1, 2, 3- t r ia z o le (2 h ) Colorless solid. Yield 0.728 g (93.4 %). 1H NMR (300 MHz, C6D6): δ = 2.12 (3H, s, CH3), 4.91 (2H, d, 3J(H-P) = 2.4 Hz, CH2O), 4.98-5.95 (2H, m, CH2), 6.80-7.78 (m, 17 H, CAr and Htrz), ppm. 13C NMR (75.7 MHz, C6D6): δ = 21.0 (CH3), 53.4 (CH2), 58.8 (d, 2J(C,P) = 4.3 Hz, CH2), 122.5 (d, J = 6.8 Hz, CAr), 122.6 (C5trz), 125.3 (d, J = 12 Hz, CAr), 126.6 (d, J = 3.4 Hz, CAr), 127.4 (d, J = 10 Hz, CAr), 128.8 (d, J = 8.9 Hz, CAr), 128.7 (CAr), 129.7 (CAr), 130.8 (d, J = 18 Hz, CAr), 131.5 (q, CAr), 132.5 (q,

ACCEPTED MANUSCRIPT Tetrahedron

4.7. Synthesis of iodides 3a-b. General procedure.

4.8.1.1-Benzyl-4-(diphenylphosphinoxymethyl)-5diphenylphosphino- 1H-1,2,3-triazole (5a) Colorless solid, yield 0.819 g (98 %). 1H NMR (500 MHz, CDCl3): 4.13 (2H, d, 3J(H-P) = 7.5 Hz, CH2 O), 5.90 (2H, s, CH2), 6.95-7.38 (m, 25 H, CHAr) ppm. 13C NMR (125 MHz, CDCl3): δ = 53.2 (d, J = 10.2 Hz, CH2), 62.2 (d, J = 21.9 Hz, CH2), 127.8 (CAr), 128.1 (d, J = 7.0 Hz, CAr), 128.3 (d, J = 6.7 Hz, CAr), 128.4 (CAr), 128.7 (d, J = 7.0 Hz, CAr), 129.1 (CAr), 129.3 (CAr), 130.6 (d, J = 21.6 Hz, CAr), 133.2 (d, J = 20.2 Hz, CAr), 133.9-134.4 (q, m, CAr), 134.9 (q, CAr), 141.5 (q, d, J = 18.4 Hz, CAr), 150.6 (q, d, J = 11.0 Hz, CAr) ppm. 31P NMR (121.5 MHz, C6D6): δ = -20.8, 130.0 ppm. MS (EI, 70 eV): m/z (%) = 557 (5) [M]+, 314 (10) [M-Ph2PO-N2]+, 201 (52) [Ph2PO]+, 91 (100). HRMS (ESI) for C34H30N3OP2 found: 558.18587 [M+H]+; calcd. 558.18587 [M+H]+.

4.8.2. 1-(4-Methylbenzyl)-4-(diphenylphosphinoxymethyl)-5diphenylphosphino-1H-1,2,3-triazole (5b) Colorless solid, yield 0.840 g (98 %). 1H NMR (300 MHz, C6D6): δ = 2.04 (3H, s, CH3), 4.55 (2H, d, 3J(H-P) = 7.6 Hz, CH2O), 5.49 (2H, s, CH2), 6.76 (2H, d, J = 7.9 Hz, CHAr), 6.927.71 (m, 22 H, CHAr), ppm. 13C NMR (75.5 MHz, C6D6): δ = 20.9 (CH3), 52.9 (d, J = 10.2 Hz, CH2), 62.8 (d, J = 21.9 Hz, CH2), 128.2 (d, J = 1.5 Hz, CAr), 128.5 (d, J = 6.8 Hz, CAr), 128.9 (d, J = 7.6 Hz, CAr), 129.2-129.3 (m, CAr), 131.1 (d, J = 21.8 Hz, CAr), 132.8 (q, CAr), 133.5 (d, J = 20.6 Hz, CAr), 134.4-135.0 (q, m, CAr), 137.5 (q, CAr), 142.5 (q, d, J = 19.5 Hz, CAr), 151.0 (q, d, J = 11.2 Hz, CAr) ppm. 31P NMR (121.5 MHz, C6D6): δ = 20.7, 129.9 ppm. MS (EI, 70 eV): m/z (%) = 571 (6) [M]+, 370 (23) [M-Ph2PO]+, 201 (72) [Ph2PO]+, 183 (100), 105 (71). HRMS (ESI) for C35H32N3OP2 found: 572.2022 [M+H] +; calcd. 572.2015 [M+H]+. HRMS (ESI) for C35H31N3NaOP2 found: 594.18434 [M+Na] +, calcd. 594.18346 [M+Na]+.

M AN U

1.6 M n-BuLi in THF (1.88 mL, 0.003 mol) was added to a solution of the relevant triazole (0.0015 mol) in THF (20 mL) at 78 °C. The resulting red-orange mixture was stirred for 30 min at room temperature. Afterwards, the reaction mixture was cooled to -78 °C and a solution of I2 (0.381 g, 0.0015 mol) in 10 ml THF was added slowly. The mixture was stirred at ambient temperature overnight and then the reaction was quenched with aqueous NH4Cl solution (10 ml). The product was extracted with diethyl ether (3×50 mL). The organic layer was washed with an aqueous solution of Na2S2O3 (10 mL) and brine (3×100 mL). The organic phase was dried over Na2SO4 and evaporated under reduced pressure. The residue was crystallized from ethyl acetate to give the product as light yellow crystals.

was transferred into toluene (10 mL) and the solution was filtered to give the pure product in nearly quantitative yield.

RI PT

CAr), 133.6 (q, d, J = 23.4 Hz, CAr), 138.2 (q, CAr), 144.8 (q, d, J(CP) = 4.4 Hz, CAr), 148.0 (q, d, J(CP) = 2.2 Hz, CAr), 149.5 (q, d, J(CP) = 5.3 Hz, CAr), 31P NMR (121.5 MHz, C6D6): δ = 152.1 ppm. MS (EI, 70 eV): m/z (%) = 518 (11) [M + H]+, 517 (34) [M]+, 332 (94) [binaphthdioxy-PO: C20H12O3P], 286 (97) [binaphthdioxy]+, 105 (100). HRMS (ESI) for C31H25N3O3P found: 518.16347 [M+H]+, calcd. 518.1628 [M+H]+. HRMS (ESI) for C31H24FN3NaO3P found: 540.14582 [M+Na]+, calcd. 540.14475 [M+Na]+.

SC

8

4.7.1. 1-Benzyl-4-(hydroxymethyl)-5-iodo-1H-1,2,3-triazole (3a)

TE D

Light yellow crystals. Yield: 0.393 g (83.1 %) mp (decomp.) 120 °C. 1H NMR (300 MHz, CDCl3): δ = 3.35 (1H, br. s, OH), 4.60 (2H, s, CH2), 5.47 (2H, s, CH2), 7.14-7.28 (5H, m, CAr) ppm. 13 C NMR (75.5 MHz, CDCl3): δ = 54.3 (CH2), 56.5 (CH2), 78.8 (q, C5trz), 127.9 (CAr), 128.6 (CAr), 129.0 (CAr), 134.1 (q, CAr), 151.2 (q, CAr) ppm. MS (EI, 70 eV): m/z (%) = 315 (0.5) [M]+, 188 (78) [M–I]+, 91 (100). HRMS (ESI) for C10H11IN3O 315.9946 found: [M+H]+, calcd. 315.9941 [M+H]+. HRMS (ESI) for C10H10IN3NaO found: 337.9766 [M+Na]+, calcd. 337.9761 [M+Na]+.

EP

4.7.2. 1-(4-Methylbenzyl)-4-(hydroxymethyl)-5-iodo-1H-1,2,3triazole (3b)

AC C

Light yellow crystals. Yield: 0.420 g (82.5 %) mp (decomp.) 152 °C. 1H NMR (300 MHz, CDCl3): δ = 2.24 (3H, s, CH3), 3.05 (1H, br. S, OH), 4.62 (2H, s, CH2), 5.45 (2H, s, CH2), 7.07 (2H, s, CAr), 7.09 (2H, s, CAr), ppm. 13C NMR (75.5 MHz, CDCl3): δ = 21.2 (CH3), 54.1 (CH2), 56.5 (CH2), 78.8 (q, C5trz), 127.9 (CAr), 129.5 (CAr), 131.1 (q, CAr), 138.4 (q, CAr), 151.2 (q, CAr) ppm. HRMS (ESI) for C11H13IN3O found: 330.00962 [M+H]+, calcd. 330.00978 [M+H]+. HRMS (ESI) for C11H12IN3NaO found: 351.99182 [M+Na]+; calcd. 351.99173 [M+Na]+.

4.8. Synthesis of bidentate hybrid ligands 5a-f. General procedure 1.6 M n-BuLi in THF (1.88 ml, 0.003 mol) was added to a solution of the relevant triazole (0.0015 mol) in THF (20 mL) at 78 °C. The resulting red mixture was stirred for 30 min at ambient temperature. Afterwards, the reaction mixture was cooled to -78 °C and a solution of diphenylchlorophosphine (0.66 g, 0.003 mol) in THF (10 ml) slowly added at -78 °C. The mixture was stirred overnight at ambient temperature. The solvent was then evaporated under reduced pressure. The residue

4.8.3. 1-(4-Methylbenzyl)-4-[bis[3,5-bis(trifluoromethyl) phenyl]-phosphinoxymethyl)-5-[bis(3,5-bis(trifluoromethyl) phenyl)-phosphino]-1H-1,2,3-triazole (5c) Colorless solid, yield 1.589 g (95 %). 1H NMR (300 MHz, CDCl3): δ = 2.00 (3H, s, CH3), 4.30 (2H, d, 3J(H-P) = 11.9 Hz, CH2O), 5.75 (2H, s, CH2), 6.70 (2H, d, J = 7.7 Hz, CHAr), 6.83 (2H, d, J = 8.1 Hz, CHAr), 7.34-7.82 (m, 12 H, CHAr) ppm. 13C NMR (125 MHz, CDCl3): δ = 20.9 (CH3), 52.8 (d, J = 10.1 Hz, CH2), 63.2 (d, J = 22.4 Hz, CH2), 120.4 (d, J = 23.9 Hz, CAr), 124.2-124.9 (br, m, CAr), 126.4-126.8 (br, m, CAr), 127.4 (CAr), 128.7 (CAr), 129.1 (CAr), 129.0 (d, J = 17.1 Hz, CAr), 129.5-130.3 (br, m, CAr), 130.6-131.6 (m, CAr), 131.6-133.5 (m, CAr), 137.4 (d, J = 17.9 Hz, CAr), 143.1 (CAr), 142.3 (d, J = 20 Hz, CAr), 143.1 (CAr), 143.5 (CAr), 144.6 (CAr) ppm. 31P NMR (121.5 MHz, CDCl3): δ = -35.9, 114.6 ppm. 19F NMR (282 MHz, CDCl3): δ = - 63.2, -63.4 ppm. MS (EI, 70 eV): m/z (%) = 1115 (3) [M]+, 614 (13) [M – Ar2PO-N2]+, 473 (41) [Ar2PO]+, 457 (25) [Ar2P]+, 105 (100). HRMS (ESI) for C43H24F24N3NOP2 found: 1116.1009 [M+H]+, calcd. 1116.1006 [M+H] +.

4.8.4. 1-(4-Fluorobenzyl)-4-(diphenylphosphinoxymethyl)-5diphenylphosphino-1H-1,2,3-triazole (5d)

ACCEPTED MANUSCRIPT 9 Colorless solid, yield 1.233 g (97 %). 1H NMR (300 MHz, C6D6): δ = 4.54-4.81 (2H, m, CH2), 4.89-5.12 (2H, m, CH2), 5.15 (2H, d, 3J(H-P) = 14.7 Hz), 6.95-7.78 (m, 29 H, Ar), ppm. 13C NMR (75.5 MHz, C6D6): δ = 50.7 (CH2O), 52.1 (CH2 O), 56.5 (d, 2 J(C,P) = 2.8 Hz, CH2O), 121.3-122.4 (m, CAr), 125.1-125.7 (m, CAr), 126.6 (d, J = 2.6 Hz, CAr), 126.9 (d, J = 3.5 Hz, CAr), 127.3 (t, J = 9.1 Hz, CAr), 127.8 (CAr), 128.3 (CAr), 128.6 (d, J = 14 Hz, CAr), 128.8 (d, J = 14 Hz, CAr), 129.3 (CAr), 130.7 -131.2 (m, CAr), 133.7 (q, CAr), 136.5 (q, CAr), 141.8 (q, d, J = 4.4 Hz, CAr), 146.2 (q, d, J = 2.4 Hz, CAr), 146.7 (q, d, J = 2.2 Hz, CAr), 147.5 (q, d, J = 5.3 Hz, CAr), 148.2 (q, d, J = 5.3 Hz, CAr), 31P NMR (121.5 MHz, C6D6): δ = 149.8, 150.7 ppm. MS (EI, 70 eV): m/z (%) = 583 (11), 332 (85), 286 (100) [binaphthdioxy]+. HRMS (ESI) for C51H36N3O6P2 found: 848.20786 [M+H]+, calcd. 848.20739 [M+H]+. HRMS (ESI) for C51H35N3NaO6P2 found: 870.19055 [M+Na] +, calcd. 870.18933 [M+Na]+.

RI PT

Colorless solid, yield 0.837 g (97 %). 1H NMR (300 MHz, C6D6): δ = 4.55 (2H, d, 3J(H-P) = 7.9 Hz, CH2O), 5.35 (2H, s, CH2), 6.78-6.74 (2H, m, CHAr), 6.94-7.70 (m, 22 H, CHAr) ppm. 13 C NMR (121.5 MHz, C6D6): δ = 52.2 (d, J = 10 Hz, CH2), 62.7 (d, J = 22 Hz, CH2), 115.3 (Co-F, d, 2J(C,F) = 21.8 Hz), 128.4 (d, J = 6.8 Hz, CAr), 128.9 (d, J = 7.6 Hz, CAr), 129.4 (d, J = 6.8 Hz, CAr), 129.3 (q, Cp-P), 129.4 (q, Cp-P), 130.4 (q, Cp-F), 131.0 (d, J = 21.8 Hz, CAr), 133.5 (d, J = 20 Hz, CAr), 135.6-136.1 (q, m, CAr), 142.4 (q, CP, d, 1J(C,P) = 19 Hz, CAr), 151.1 (q, d, J = 11 Hz, CAr), 162.5 (q, CF, d, 1J(C,F) = 246 Hz) ppm. 31P NMR (121.5 MHz, C6D6): δ -= 35.3, 114.9 ppm. 19F NMR (282 MHz, C6D6): δ = 115.0 ppm. MS (EI, 70 eV): m/z (%) = 576 (6) [M+1]+, 575 (15) [M]+, 498 (16), 482 (16), 362 (47) [M-Ph2P-N2]+, 201 (95) [Ph2PO]+, 109 (100). HRMS (ESI) for C34H29FN3OP2 found: 576.17600 [M+H]+, calcd. 576.17644 [M+H] +. HRMS (ESI) for C34H28FN3NaOP2 found: 598.15755 [M+Na]+, 598.15838 (calcd.) [M+Na]+.

Colorless solid, yield 1.629 g (96 %). 1H NMR (300 MHz, C6D6): δ = 4.35 (2H, d, J = 10.9 Hz, CH2O), 4.92 (2H, d, J = 11.9 Hz, CH2O), 5.04 (2H, s, CH2), 6.79-7.68 (m, 9 H, CHAr), 7.71 (4H, d, J = 6.8 Hz, CHAr), 7.93 (4H, d, J = 6.4 Hz, CHAr) ppm. 13 C NMR (75.5 MHz, C6D6): δ = 52.4 (CH2), 58.9 (d, 2J(C,P) = 24 Hz, CH2), 63.5 (d, 2J(C,P) = 24 Hz, CH2), 121.5 (q, d, J = 17.1 Hz, CAr), 123.8-124.7 (br, m, 4 C, CAr), 125.1 (d, J = 17.4 Hz, CAr), 127.1 (CAr), 128.3 (CAr), 128.7 (CAr), 129.1 (CAr), 129.5-130.3 (br, m, 8C, CAr), 130.9 (q, d, J = 7 Hz, CAr), 131.6-133.5 (m, CAr), 134.3 (q, CAr), 138.0 (q, d, J = 19.0 Hz, CAr), 142.9 (q, d, J = 24.3 Hz, CAr), 143.6 (q, d, J = 6.1 Hz, CAr), 144.2 (q, d, J = 24.7 Hz, CAr) ppm. 31P NMR (121.5 MHz, C6 D6): δ = 122.3, 122.8 ppm, 19F NMR (282 MHz, CDCl3): δ = -63.0, -63.1 ppm. HRMS found: 1132.09668 [M+H]+, (ESI) for C43H24F24N3O2P2 + 1132.0955 calcd. [M+H] .

M AN U

The synthesis was carried out according to the slightly modified procedure of Liu.[18] Benzyl bromide (22.23 g, 15.44 mL, 0.13mol) was added to the suspension of but-2-yne-1,4-diol (8.6g, 0.1mol) and sodium azide (7.8g, 0.12mol) in 50mL DMF at room temperature (attention, self-warming). The mixture was stirred at 130 °C for 18 h. Colorless crystals, yield 53 %, mp 104.5-105.5. 1H NMR (300.1 MHz, CDCl3): δ = 4.45 (2H, s, OCH2), 4.53 (2H, s, OCH2), 4.72-5.21 (2H, br. s, OH), 5.45 (2H, s, CH2Ph), 7.08-7.25 (5H, m, CHAr), 13C NMR (75.5 MHz, CDCl3): δ = 52.0 (CH2O), 52.3 (CH2O), 55.1 (CH2Ph), 127.6 (CAr), 128.3 (CAr), 128.9 (CAr), 134.3 (q, CAr), 134.7 (q, CAr), 145.1 ( q, CAr).

SC

4.10.3. 1-Benzyl-4,5-bis[3,5-bis(trifluoromethyl)phenyl]-1H1,2,3-triazole (8c)

4.9. 1-Benzyl-4,5-di(hydroxymethyl)-1H-[1,2,3]triazole (7)

TE D

4.10. Synthesis of bidentate ligands 8a-c. General procedure

The synthesis of bidentate ligand 8a-c was performed analog to the synthesis of ligands 5a-d. Yields were nearly quantitative.

4.10.1. 1-Benzyl-4,5-bis(diphenylphosphinoxymethyl)-1H-1,2,3triazole (8a)

AC C

EP

Colorless solid, yield 0.873 g (99 %). 1H NMR (300 MHz, C6D6): δ = 4.66 (2H, d, 3J(H-P) = 9.0 Hz), 5.15 (2H, d, 3J(H-P) = 10.0 Hz), 5.20 (2H, s, CH2), 6.95-7.20 (m, 17 H, Ar), 7.44-7.52 (4H, m, Ar), 7.63-7.71 (4H, m, Ar) ppm. 13C NMR (75.5 MHz, C6D6): δ = 50.1 (CH2), 57.1 (dd, J = 2.2 Hz, 2J(C,P) = 22.5 Hz, CH2), 61.6 (d, 2J(C,P) = 22.2 Hz, CH2), 127.6 (CAr), 128.1 (CAr), 128.5 (d, Cm-P, 3J(C,P) = 7 Hz, CAr), 128.7 (d, Cm-P, 3J(C,P) = 7 Hz, CAr), 127.6 (CAr), 128.0 (CAr), 128.5 (CAr), 129.6 (d, Co-P, d, 2J(C,P) = 22 Hz, CAr), 129.7 (d, Co-P, d, 2J(C,P) = 22 Hz, CAr), 131.0 (q, d, J = 9.4 Hz, CAr), 134.1 (q, CAr), 139.9 (q, d, 2J(C,P) = 18.5 Hz, CAr), 140.9 (q, d, 2J(C,P) = 18.5 Hz, CAr), 143.1 (q, d, J = 8.3 Hz, CAr) ppm. 31P NMR (121.5 MHz, C6D6): δ = 128.9, 131.7 ppm. MS (EI, 70 eV): m/z (%) = 588 (3) [M+1]+, 587 (4) [M]+, 386 (6) [M-Ph2PO]+, 358 (29) [M-Ph2PO-N2]+, 201 (91) 91 (100). HRMS (ESI) for C35H32N3OP2 found: 588.1973 [M+H] +, calcd. 588.1964 [M+H]+. HRMS (ESI) for C35H31N3NaOP2 found: 610.1788 [M+Na]+; calcd. 610.1784 [M+Na]+.

4.10.2. 1-Benzyl-4,5-bis[(dinaphtho[1,2-f:2´,1´d][1,3,2,] dioxaphosphephin-4-yloxy)methyl]-1H-1,2,3-triazole (8b)

4.11. Synthesis of Pt(5a-b)Cl2 and Pt(8a) complex. General procedure To a stirred suspension of Pt(COD)Cl2 (0.187 g, 0.0005 mol) in CH2Cl2 (8 mL) a solution of ligand 5a or 5b (0.0005 mol) in CH2Cl2 (8 mL) was added dropwise and the reaction mixture was stirred overnight at ambient temperature. Then the solvent was evaporated and the obtained solid was dried in vacuum. Yields were nearly quantitative.

4.11.1. Pt(5a)Cl2 Colorless powder. 1H NMR (300 MHz, CDCl3): δ = 4.58 (2H, s, CH2), 5.37 (2H, (d, 3J(H-P) = 17.0 Hz, CH2O), 6.42 (2H, d, J = 7.6 Hz, CHAr), 7.95-7.53 (m, 23 H, CHAr), ppm. 13C NMR (75.5 MHz, CDCl3): δ = 54.1 (CH2), 61.8 (CH2), 124.8 (q, CAr), 125.7 (q, CAr), 127.3 (CAr), 128.1 (d, J = 12.4 Hz, CAr), 128.4 (CAr), 128.5 (CAr), 128.7 (CAr), 128.8 (d, J = 12.6 Hz, CAr), 130.8 (q, CAr), 131.8-132.0 (m, CAr), 132.1 (d, J = 12.0 Hz, CAr), 133.3 (q, CAr), 150.9 (q, d, J = 18.2 Hz, CAr) ppm. 31P NMR (121.5 MHz, CDCl3): δ = -11.9 (dd, 1J(PPt) = 3726.8 Hz, 2J(PP) = 15.0 Hz), 91.2 (dd, 1J(PPt) = 3868.6 Hz, 2J(PP) = 15.0 Hz). HRMS (ESI) for C34H29ClN3OP2Pt found: 788.11108 [M-Cl]+; calcd. 788.11171 [M-Cl]+, HRMS (ESI) for C34H29Cl2N3NaOP2Pt found: 846.07007 [M+Na] +, calcd. 846.06945[M+Na]+.

4.11.2. Pt(5b)Cl2

ACCEPTED MANUSCRIPT Tetrahedron

4.11.3. Pt(8a)Cl2

Acknowledgments The authors are grateful to by Evonik Oxeno GmbH for financial support of this work. We thank Dr. C. Fischer, S. Buchholz, A. Lehmann and K. Romeike (all at the LeibnizInstitut für Katalyse e.V.) for their excellent analytical support.

References and notes 1.

2.

Phosphorus(III) Ligands in Homogeneous Catalysis, Design and Synthesis, P. C. J. Kamer, P. W. N. M. van Leeuwen (Eds.), Wiley-VCH, 2012. a) H. C. Kolb, M. G. Finn, B. K. Sharpless, Angew.Chem. Int. Ed. 2001, 40, 2004-2021; b) H. C. Kolb, B. K. Sharpless, Drug Discovery Today 2003, 8, 1128-1137. a) V. V. Rostovtsev, L. G. Green, V. V. Fokin, K. B. Sharpless, Angew. Chem. Int. Ed. 2002, 41, 2596-2599; b) C. W. Tornøe, C. Christensen, M. Meldal, J. Org. Chem. 2002, 67, 3057-3064; c) L. V. Lee, M. L. Mitchell, S.-J. Huang, V. V. Fokin, K. B. Sharpless, C.-H. Wong, J. Am. Chem. Soc. 2003, 125, 9588-9589; d) S. G. Agalave, S. R. Maujan, V. S. Pore, Chem. Asian J. 2011, 6, 26962718. a) D. Liu, W. Gao, Q. Dai, X. Zhang, Org. Lett. 2005, 4907-4910; b) Q. Dai, W. Gai, D. Liu, L. M. Kapes, X. Zhang, J. Org. Chem. 2006, 71, 3928-3934. S.-i. Fukuzawa, H. Oki, M. Hosaka, J. Sugasawa, S. Kikuchi, Org. Lett. 2007, 5557-5560. R. J. Detz, S. Arevalo Heras, R. de Gelder, P. W. N. M. van Leeuwen, H. Hiemstra, J. N. H. Reek, J. H. van Maarseveen, Org. Lett. 2006, 8, 3227-3230. a) E. M. Schuster, M. Botoshansky, M. Gandelman, Angew. Chem. Int. Ed. 2008, 47, 4555-4558; b) E. M. Schuster, M. Botoshansky, M. Gandelman, Organometallics 2009, 28, 70017005; c) E. M. Schuster, G. Nisnevich, M. Botoshansky, M. Gandelman, Organometallics 2009, 28, 5025-5031. F. Dolhem, M. J. Johansson, T. Antonsson, N. Kann, J. Comb. Chem. 2007, 9, 477-486. Y. Matano, M. Nakashima, A. Saito, H. Imahori, Org. Lett. 2009, 11, 3338-3341. Q. Zhang, J. M. Takacs, Org. Lett. 2008, 10, 545-548. In Ref. 7, among more than 20 phosphines-boranes also one BH3protected phosphine phosphite is mentioned. (a) Rhodium Catalyzed Hydroformylation, van Leeuwen, P. W. N. M.; Claver, C., Eds.; Kluver Academic Publishers: Dordrecht Netherlands; 2000; (b) R. Franke, D. Selent, A. Börner, Chem. Rev. 2012, 112, 5675–5732. For reviews, see: a) S. Lühr, J. Holz, A. Börner, ChemCatChem 2011, 3, 1708-1730; b) Phosphorus Ligands in Asymmetric Catalysis (Ed.: A. Börner), Wiley-VCH, Weinheim, 2008; c) N. V. Dubrovina, I. A. Shuklov, A. Börner in Targets in Heterocyclic Systems (Eds.: O. A. Attanasi, D. Spinelli), Royal Society of Chemistry, Cambridge, 2008, vol. 12, 149-184. See also: a) I. A. Shuklov, N. V. Dubrovina, E. Barsch, R. Ludwig, D. Michalik A. Börner, Chem. Comm. 2009, 1535-1537; b) M.-N. Birkholz, N. V. Dubrovina, H. Jiao, D. Michalik, J. Holz, R. Paciello, B. Breit, A. Börner, Chem. Eur. J. 2007, 13, 5896-5907; c) N. V. Dubrovina, I. A. Shuklov, M.-N. Birkholz, D. Michalik, R. Paciello, A. Börner, Adv. Synt. Catal. 2007, 349, 2183-2187; d) N. Dubrovina, A. Boerner, in Catalysts for Fine Chemical Synthesis (Eds.: S. M. Roberts, J. Whittall) John Wiley&Sons Ltd., Chichester, 2007, vol. 5, pp 89-93. For some recent examples, see: a) I. S. Mikhel, N. V. Dubrovina, I. A. Shuklov, W. Baumann, D. Selent, H. Jiao, A. Christiansen,

M AN U

Colorless powder. 1H NMR (300 MHz, CDCl3): δ = 4.73 (2H, d, J = 8.4 Hz, CH2), 4.90 (2H, d, J = 7.8 Hz, CH2), 5.34 (2H, s, CH2, CH2Ph), 6.95 (2H, d, J = 7.8 Hz, CHAr), 7.12-7.47 (m, 19 H, CHAr), 7.61-7.70 (4H, m, CHAr) ppm. 13C NMR (75.5 MHz, CDCl3): δ = 52.8 (CH2), 59.2 (d, J = 6.4 Hz, CH2), 60.8 (d, J = 7.3 Hz, CH2), 126.4 (CAr), 127.2 (d, J = 7.8 Hz, CAr), 127.4 (d, J = 8.0 Hz, CAr), 127.7 (CAr), 127.8 (CAr), 128.1 (CAr), 129.4 (CAr), 129.6 (CAr), 130.2 (CAr), 130.3 (CAr), 130.4 (CAr), 130.6 (CAr), 131.0 (dd, J = 2.7 Hz, J = 12.0 Hz, CAr), 131.5 (d, J = 12.0 Hz, CAr), 131.9 (d, J = 12.0 Hz, CAr), 132.7 (CAr), 142.5 (d, J = 8.8 Hz, CAr) ppm. 31P NMR (121.5 MHz, CDCl3): δ = 87.06 (dd, 1 J(PPt) = 4187.9 Hz, 2J(PP) = 7.4 Hz,), 88.6 (dd, 1J(PPt) = 4216.9 Hz, 2 J(PP) = 7.4 Hz) ppm. HRMS (ESI) for C35H31ClN3O2P2Pt found: 818.11312 [M-Cl]+, cacld. 818.11772 [M-Cl]+.

128.3 (d, J = 12.3 Hz, CAr), 129.0 (CAr), 129.2 (CAr), 130.2 (q, CAr), 131.2 (q, CAr), 131.8 (d, J = 2.9 Hz, CAr), 132.1 (d, J = 2.7 Hz, CAr), 132.2 (q, CAr), 132.5 (d, J = 11.5 Hz, CAr), 133.2 (d, J = 12.2 Hz, CAr), 138.4 (q, CAr), 150.6 (q, d, J = 19.2 Hz, CAr) ppm. 31 P NMR (121.5 MHz, CDCl3): δ = 1.6 (d, 2J(PP) = 17.1 Hz), 120.6 (d, 2J(PP) = 17.8 Hz) ppm. MS (EI, 70 eV): m/z (%) = 342 (21.5) [M-Ph2PO-N2]+, 201 (40) [Ph2PO]+, 84 (100). HRMS (ESI) for C35H31ClN3OP2Pd found: 712.0723 [M-Cl]+, cacld. 712.06698 [M-Cl] +.

3.

4.

4.11.4. Pt(8b)Cl2

AC C

EP

TE D

Colorless powder. 1H NMR (300 MHz, C6D6): δ = 5.30 - 5.76 (6H, m, CH2), 6.99-7.89 (m, 29 H, CHAr), ppm. 13C NMR (75.5 MHz, C6D6): δ = 53.3 (CH2), 56.3 (CH2), 59.8 (d, J = 4.2 Hz, CH2), 125.3 (CAr), 127.2 (CAr), 127.7 (CAr), 128.2 (CAr), 128.6 (CAr), 128.7 (CAr), 129.2 (d, J = 12.4 Hz, CAr), 131.0 (d, J = 11.6 Hz, CAr), 131.5 (CAr), 131.9 (dd, J = 1.5 Hz, J = 8.6 Hz, CAr), 132.2 (dd, J = 1.6 Hz, J = 9.6 Hz, CAr), 133.1 (CAr), 137.8 (CAr), 142.3 (d, J = 3.3 Hz, CAr), 145.3 (d, J = 6.6 Hz, CAr), 145.6 (d, J = 6.4 Hz, CAr), 146.3 (d, J = 12.0 Hz, CAr), 146.7 (d, J = 12.5 Hz, CAr), 31P NMR (121.5 MHz, C6D6): δ = 88.7 ppm (br. d, 1J(PPt) = 5562 Hz, 2J(PP) = 24 Hz), 93.7 ppm (d, 1J(PPt) = 5542 Hz, 2J(PP) = 24 Hz). HRMS (ESI) for C51H36Cl2N3O6P2Pt found: 1114.10878 [M+H]+, cacld. 1114.10963 [M+H]+. HRMS (ESI) for C51H36Cl2N3NaO6P2Pt found: 1136.09469 [M+Na]+, cacld. 1136.09157 [M+Na]+.

4.11.5. Synthesis of Pd(5b)Cl2 complex

5.

6.

7.

8. 9. 10. 11. 12.

13.

To a stirred suspension of Pd(MeCN)2Cl2 (0.0571, 0.1 mmol) in CH2Cl2 (1 mL) a solution of ligand 5b (0.0259 mg, 0.1 mmol) in CH2Cl2 (2 mL) was added dropwise and the reaction mixture was stirred for 2 h. The reaction mixture became homogeneous. Then the solvent was evaporated and the obtained solid was dried in vacuum. Yield was nearly quantitative. Lightly yellow powder. 1

H NMR (300 MHz, CDCl3): δ = 2.19 ( 3H, s, CH3), 4.54 (2H, s, CH2), 5.28 (2H, (d, J = 16.8 Hz, CH2), 6.38 (2H, d, J = 8.0 Hz, CHAr), 6.84 (2H, d, J = 7.9 Hz, CHAr), 7.14-7.62 (m, 20 H, CHAr) ppm. 13C NMR (75.5 MHz, CDCl3): δ = 21.9 (CH3), 54.0 (CH2), 61.6 (d, J = 2.8 Hz, CH2), 125.4 (CAr), 126.3 (CAr), 127.6 (CAr),

RI PT

Colorless powder. 1 H NMR (300 MHz, CDCl3): δ = 2.19 (3H, s, CH3), 4.50 (2H, s, CH2), 5.36 (2H, (d, J = 17.0 Hz, CH2), 6.33 (2H, d, J = 8.1 Hz, CHAr), 6.83 (2H, d, J = 8.0 Hz, CHAr), 7.12–7.53 (m, 20 H, CHAr), ppm. 13C NMR (75.5 MHz, CDCl3): δ = 21.1 (CH3), 54.0 (CH2), 61.8 (CH2), 124.9 (q, CAr), 125.8 (q, CAr), 127.5 (CAr), 128.1 (d, J = 12.2 Hz, CAr), 128.7 (CAr), 128.8 (d, J = 12.6 Hz, CAr), 129.2 (CAr), 130.3 (q, CAr), 130.8 (q, CAr), 131.8-132.0 (m, CAr), 132.1 (d, J = 12.0 Hz, CAr), 133.3 (d, J = 11.2 Hz, CAr), 138.4 (q, CAr), 150.9 (q, d, J = 18.0 Hz, CAr) ppm. 31 P NMR (121.5 MHz, CDCl3): δ = -11.9 (dd, 1J(PPt) = 3726.8 Hz, 2 J(PP) = 15.0 Hz,), 91.2 (dd, 1J(PPt) = 3868.6 Hz, 2J(PP) = 15.0 Hz) ppm. HRMS (ESI) for C35H31ClN3OP2Pt found: 802.12843 [MCl]+, cacld. 802.12739[M-Cl] +.

SC

10

14.

ACCEPTED MANUSCRIPT 11

RI PT

lickhertom C vnsuiex.

SC

19.

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