Four-membered Rings with One Selenium or Tellurium Atom

2.09 Four-membered Rings with One Selenium or Tellurium Atom M. Koketsu and H. Ishihara Gifu University, Gifu, Japan ª 2008 Elsevier Ltd. All rights reserved. 2.09.1

Introduction

463

2.09.2

Theoretical Methods

464

2.09.3

Experimental Structural Methods

464

2.09.3.1 X-Ray Diffraction

464

2.09.3.2 NMR Spectroscopy

465

1

465 466 468

2.09.3.2.1 2.09.3.2.2 2.09.3.2.3

H NMR spectroscopy C NMR spectroscopy 77 Se NMR spectroscopy 13

2.09.3.3 Mass Spectrometry

468

2.09.3.4 Infrared Spectroscopy

468

2.09.4

Thermodynamic Aspects

469

2.09.5

Reactivity of Fully Conjugated Rings

469

2.09.6

Reactivity of Nonconjugated Rings

470

2.09.7

Reactivity of Substituents Attached to Ring Carbon Atoms

470

2.09.8

Reactivity of Substituents Attached to Ring Heteroatoms

470

2.09.9

Ring Synthesis from Acyclic Compounds

472

2.09.10

Ring Synthesis by Transformation of Another Ring

475

2.09.11

Synthesis of Particular Classes of Compounds

475

2.09.12

Important Compounds and Applications

475

2.09.13

Further Developments

475

References

476

2.09.1 Introduction This subject was covered previously in CHEC-II(1996) <1996CHEC-II(1)823>. This chapter is intended to update this previous version and to highlight major new preparations, reactions and concepts. We have provided at the beginning of each main section a short paragraph explaining the major advances since the publication of the earlier chapters and some deficiencies in CHEC-II(1996) that we have now attempted to address. Four-membered cyclic compounds with one selenium or tellurium atom are named selenetane 1, telluretane 2, selenete 3, and tellurete 4. The literature regarding those compounds is quite limited. A few examples of compounds 1 and 3, that is, threesubstituted derivatives and tungsten-pentacarbonyl- or rhenium-complexes, in particular, have been described since the publication of CHEC-II(1996) <1996CHEC-II(1)823>. Compounds 3 and 4, the unsaturated analogs of 1 and 2, have not been described since the publication of CHEC(1984) and CHEC-II(1996). No discussions on telluretane 2 and tellurete 4 were found in the literature in the period 1995–2005. In this chapter, we describe crystal structures, nuclear magnetic resonance (NMR), and syntheses of the derivatives of 1 and 3 which have been mentioned.

463

464

Four-membered Rings with One Selenium or Tellurium Atom

2.09.2 Theoretical Methods The stabilities of benzoselenete 5 and the o-quinoid form 6 were calculated and compared. With the geometry optimization of the 6-31G basis set, the benzoselenete 5 is calculated to be 58.41 kJ mol1 (13.96 kcal mol1) more stable than the o-quinoid form 6 in the ground-state S0. Bond lengths (CTSe) of the calculated value are quite similar to the observed X-ray crystallographic data <2001JA7166, 2001HCA1578>.

2.09.3 Experimental Structural Methods 2.09.3.1 X-Ray Diffraction Crystal structures of selenetane derivatives were not described in CHEC(1984) and CHEC-II(1996) (1984CHEC-I, 1996CHEC-II). For the first time in 1995, selenetane derivatives were characterized by X-ray diffraction <1995CB1149, 1995CC2461> and since then six selenetane derivatives were determined by X-ray diffraction. The bond angles, bond lengths, and torsion angles are shown in Table 1. The selenete ring of the reported compounds is almost planar, while the torsion angle of the selenetane ring is about 23 . In most cases, due to the larger radius of Se, the C4-X-C2 angle in the selenetane ring is smaller than that in the thietanes (cis 79.3 , trans 76.6 ) <1975BCJ2339, 1981BCJ3701>. Also, the structures of complexes with some metal atoms were obtained: the selenetane ring can be coordinated to tungsten <1995CB1149, 1995CC2461> or to a rhenium atom <1997CC525, 1997OM3895> via the selenium atom.

Table 1 X-ray diffraction of selenetane derivatives

Compound

Bond angle ( )

˚ Bond length (A)

Torsion angle ( )

C4–Se1–C2

Se1–C2 C4–Se1

C2–C3 C3–C4

Se1–C2–C3–C4

1.978(3)a

1.536(4)a

18.74(19)

(Se–C)

(C–C)

24.65(18)

1.93(2)

1.51(3)

1.91(2)

1.54(3)

2.032(7)

1.484(11)

2.041(6)

1.512(8)

CCDC No.

Reference

215350

2004IC5558

NDb

SIc

1997OM3895

23.6(5)

CSD-401939

1995CB1149

72.0(1)

72.2(9)

70.9(3)

(Continued)

Four-membered Rings with One Selenium or Tellurium Atom

Table 1 (Continued)

Compound

Bond angle ( )

Bond length (A˚)

Torsion angle ( )

C4–Se1–C2

Se1–C2 C4–Se1

C2–C3 C3–C4

Se1–C2–C3–C4

CCDC No.

Reference

1.92(1)

1.49(2) NDb

SIc

2001JA7166

2.00(1)

1.39(2)

2.014(2)

1.416(3) 3.44(16)

251943

2004H(62)521

1.921(2)

1.447(3)

1.953(5)

1.516(7) 5.4(5)

NDb

1995CC2461

2.061(5)

1.330(8)

70.4(6)

83.5(1)

68.9(2)

a

Averaged. No information available. c See supporting information of the literature. b

2.09.3.2 NMR Spectroscopy 2.09.3.2.1

1

H NMR spectroscopy

1

In H NMR spectra of selenetane derivatives, the H-2, H-3, and H-4 signals of the saturated selenetanes 7–8, 14–17 are observed in the range of 2.8–3.7 ppm, while those of the unsaturated selenetes 12 and 18 are in the range of 5.5 ppm (Table 2). Table 2 Compound

1

H NMR data for selenetane derivatives H-2 (ppm)

H-3 (ppm)

H-4 (ppm)

Reference

3.14

3.14

2004IC5558

3.20

3.58

1997OM3895

5.66

5.85

(C(C6H5)H)

(C(SCH3)H)

1995CB1149

(Continued)

465

466

Four-membered Rings with One Selenium or Tellurium Atom

Table 2 (Continued) Compound

H-2 (ppm)

H-3 (ppm)

H-4 (ppm)

Reference

4.41  0.95 2.81  0.24 (C(C6H5)H)

3.56  0.12

1995CB1149 (CH2)

4.65 5.57

3.55

(C(OEt)H)

3.99

(C(C6H5)H)

1996CB1169

2.93

3.68

5.40

(H5a)

(H3)

(H4)

3.43 (H5b)

3.71

5.59

(H3)

(H4)

4.21

5.40

(H3)

(H4)

2000CAR107

3.16 (H5a) 2000CAR107 3.39 (H5b)

2.89 (H5a) 2004CAR1787

2.09.3.2.2 13

3.45 (H5b)

5.52

1995CC2461

5.55  0.025

1995CC2461

13

C NMR spectroscopy

In C NMR spectra of selenetane derivatives, the C-2, C-3, and C-4 signals of the saturated selenetanes 7, 14–17 are observed in the range of 18–84 ppm, while those of the unsaturated selenetes 11, 12, and 18–20 are in the range of 50–89 ppm (single bond) and 128–150 ppm (double bonds) (Table 3).

Four-membered Rings with One Selenium or Tellurium Atom

Table 3 Compound

13

C NMR data for selenetane derivatives C-2 (ppm)

C-3 (ppm)

C-4 (ppm)

Reference

28.7

54.4

28.7

2004IC5558

62.2

1995CB1149

58.0

40.9

83.1 44.9

[C(H)OEt]

1996CB1169 [C(H)Ph]

34.62

81.42

18.43

(H3)

(H4)

(H5)

35.97

83.99

21.66

(H3)

(H4)

(H5)

33.59

82.18

18.07

(H3)

(H4)

(H5)

148.6  0.7

140.3  0.3

112.5  0.05

2004H(62)521

136.8

143.5

50.8

1995CC2461

144.2  0.85

142.4  0.25

63.5  1.5

1995CC2461

2000CAR107

2000CAR107

2004CAR1787

(Continued)

467

468

Four-membered Rings with One Selenium or Tellurium Atom

Table 3 (Continued) Compound

2.09.3.2.3

C-2 (ppm)

C-3 (ppm)

C-4 (ppm)

Reference

128.3

149.8

83.0

2001JA7166

130.3

149.2

88.5

2001JA7166

77

Se NMR spectroscopy

Only for three selenete complexes 12a, 12b, and 18 have 77Se NMR data been reported <1995CC2461>. The chemical shifts of 77Se NMR spectra in the selenetes are compiled in Table 4. Table 4

77

Se NMR data for selenetes 77

Compound

Se chemical shifts

Solvent

ppm

Reference

CDCl3

745

1995CC2461

CDCl3

762

1995CC2461

CDCl3

833

1995CC2461

2.09.3.3 Mass Spectrometry No discussions on mass spectrometry related to four-membered cyclic compounds with one selenium or tellurium atom were found in the literature in the period 1995–2005.

2.09.3.4 Infrared Spectroscopy No discussions on infrared spectroscopy related to four-membered cyclic compounds with one selenium or tellurium atom were found in the literature for the period 1995–2005.

Four-membered Rings with One Selenium or Tellurium Atom

2.09.4 Thermodynamic Aspects No discussions on thermodynamic aspects related to four-membered cyclic compounds with one selenium or tellurium atom were found in the literature for the period 1995–2005.

2.09.5 Reactivity of Fully Conjugated Rings 2-Iminoselenete 11 has been reacted with morpholine or cyclohexylamine to afford 2-diaminomethylene-3-oxobutane selenoamides. The products exist in an enolized form (Scheme 1) <2004H(62)521>.

Scheme 1

The decomplexation of the selenete ligand of 12 has been achieved with NEt4Br to give a mixture of selenete 18 and 3,4-dihydro-1,2-diselenine 21. The structure of compound 21 was confirmed by an X-ray diffraction. Formation of diselenine 21 proceeds by ring opening of selenete 18 to form the ,-unsaturated thioselenocarboxylic ester 22 which then serves both as a 4p selenadiene (CTC–CTSe) and as a 2p dienophile (Se ¼ C) in a ‘head-to-head’ Diels–Alder reaction to form 21. Ring opening and cycloaddition are highly regio- and stereoselective (Scheme 2) <1995CC2461>.

Scheme 2

469

470

Four-membered Rings with One Selenium or Tellurium Atom

2.09.6 Reactivity of Nonconjugated Rings Complex Re2(CO)9-3,3-dimethylselenetane 8 has been obtained by reaction of Re2(CO)9NCMe with 3,3-dimethylselenetane 23 in hexane under reflux conditions in 88% yield (Equation 1). 3,3-Dimethylselenetane 23 has also been cyclooligomerized catalytically by the complex Re2(CO)9-3,3-dimethylselenetane 8. It serves as a catalyst for the ring-opening macrocyclization of the 3,3-dimethylselenetane 23 to afford 3,3,7,7-tetramethyl-1,5-diselenacyclooctane 24, 3,3,7,7,11,11hexamethyl-1,5,9-triselenacyclododecane 25 and 3,3,7,7,11,11,15,15-octamethyl-1,5,9,13-tetraselenacyclohexadecane 26 (Scheme 3). All three macrocycles have been characterized by X-ray diffraction. The mechanism involves a series of ringopening additions of 23 to the 3,3-dimethylselenetane ligand in 8. The catalytic cycle is completed by exchange of the macrocycle with another 3,3-dimethylselenetane molecule (Scheme 4) <1997CC525, 1997OM3895>.

ð1Þ

Scheme 3

Acylation of the C-4 hydroxy group of 27 has been carried out using LHMDS/methyl chloroformate. However, the isolation of the 4-acyl analog 28 was difficult and, instead, a mixture of 28 and the ring-opened derivative 29 was tentatively identified. The presumed compound 28 was unstable and was converted to 29 either on attempted purification or on standing in a CDCl3 solution (Scheme 5) <1999JOC2694>.

2.09.7 Reactivity of Substituents Attached to Ring Carbon Atoms No discussions on these reactions related to four-membered cyclic compounds with one selenium or tellurium atom were found in the literature for the period 1995–2005.

2.09.8 Reactivity of Substituents Attached to Ring Heteroatoms Pentacarbonyltungsten-coordinated selenete 14 has been treated with NEt4Br to lead to decomplexation of the selenete to give selenete 18 (Equation 2) <1995CC2461>.

ð2Þ

Four-membered Rings with One Selenium or Tellurium Atom

Scheme 4

Scheme 5

471

472

Four-membered Rings with One Selenium or Tellurium Atom

2.09.9 Ring Synthesis from Acyclic Compounds The preparations of the parent selenetane (SeC3H6 1) and telluretane (TeC3H6 2) have been described in CHECII(1996) <1996CHEC-II(1)823>. They have been prepared by the reaction of disodium chalcogenide with 1,3-dibromopropane. Using a similar reaction, spiroselenetane 7 has been obtained. Treatment of a heterogeneous milky white suspension, prepared from superhydride (Li(C2H5)3BH) and selenium powder, and 1,3-dibromo-2,2-bis(bromomethyl)propane affords spiroselenetane, 2,6-diselenaspiro[3.3]heptane, Se2C5H8 7 in 70% yield (Scheme 6) <2004IC5558>.

Scheme 6

Reactions of 2-(3-hydroxy-3-phenylpropylseleno)benzoxazole with KH in tetrahydrofuran (THF) give selenetane 31. In the cases of tert-alcohols (R1 ¼ C2H5 or CH2Ph), complex mixtures of products and no expected selenetane 31 are obtained because of steric hindrance at the reaction site. The formation of a selenetane is explained by a spiro intermediate which is converted into a selenolate anion. Intramolecular displacement of 30 gives the selenetane 31 (Scheme 7) <1998H633>.

Scheme 7

Pentacarbonyltungsten-coordinated selenobenzaldehydes, (CO)5W[SeTCH(p-RC6H4)] (R ¼ OMe, H, CF3) 32, react with ButSCUCSBut (2.5 equiv) by addition of the CUC to the SeTC bond to give 2H-selenete complexes 12 (Scheme 8) <1995CC2461>.

Scheme 8

Four-membered Rings with One Selenium or Tellurium Atom

Pentacarbonyl(selenobenzaldehyde)tungsten, (CO)5W[SeTCH(C6H5)] 32, reacts with ethyl vinyl ether by [2þ2] cycloaddition of the CTC to the SeTC bond to give selenetane 14 (Equation 3) <1996CB1169>.

ð3Þ

Reaction of pentacarbonyltungsten-coordinated selenobenzaldehyde, [(CO)5W(SeTCHPh)] 32, with eightfold excess of 1-methylthio-1-propyne (MeCUCSMe) 33 gives three complexes: the thioselonocarboxylic ester complex as a mixture of the (E)- and (Z)- (CTC) isomers 34, a selenetane complex 9, and a dihydrodiselenine complex 35. The product distribution depended on the ratio 32:33 and on the solvent (Equation 4) <1995CB1149>.

ð4Þ

Aryl isoselenocyanates 4-RC6H4NCSe (R ¼ H, Br, Cl, MeO) (prepared by selenation and dehydration of N-arylformamides) undergo regioselective cycloaddition reactions with 4-diethylamino-3-butyn-2-one in refluxing THF yielding N-arylselenetimines 11 (Scheme 9) <2004H(62)521>.

Scheme 9

Reaction of 1,1,3,3-tetramethylindane-2-selenone with o-trimethylsilylphenyl trifluoromethanesulfonate in the presence of tetrabutylammonium fluoride affords benzoselenete 19 in 70% yield (Equation 5). Another sterically crowded selenone, di-tert-butyl selenoketone, gives the corresponding benzoselenete 20 in 45% yield (Equation 6). When 1,1,3,3-tetramethylindane-2-selenone is treated with benzenediazonium-2-carboxylate in refluxing benzene, compound 19 is obtained (27%) along with the rearranged product 36 in 7% yield (Equation 7) <2001JA7166>.

473

474

Four-membered Rings with One Selenium or Tellurium Atom

ð5Þ

ð6Þ

ð7Þ

Methyl 2,3-anhydro-5-O-mesyl--D-ribo-furanosides 37 are treated with sodium hydrogen selenide to give selenabicycloheptanes. Reaction of furanoside 37 affords both selenetane 15 and selenolane 38 (Equation 8). Reaction of -furanoside 39 gave only selenetane 16. Selenolane 38, a bicyclo[2.2.1]heptane derivative, is not formed from 39 (Equation 9). Selenetane 17 is obtained from methyl 2,3-anhydro--D-ribo-furanoside 40 via the dimethylate (Equation 10). On the other hand, the analogous reaction of furanoside 37 with sodium hydrogen telluride gives the elusive tellurabicyclo[2.2.1]heptane 41 (Equation 11) <1999PS429, 2004CAR1787>.

ð8Þ

ð9Þ

ð10Þ

ð11Þ

Reaction of 37 with sodium hydrogen selenide affords selenetane 15, selenolane 38, and diselenide 42 (Equation 12). The ratio of the products was dependent on the reaction temperature <2000CAR107>.

Four-membered Rings with One Selenium or Tellurium Atom

ð12Þ

Treatment of a THF solution of the 5-iodo-20-epoxy derivative 43 with Li2Se afforded the 5,20-seleno derivative 27 in 67% yield (Equation 13) <1999JOC2694>.

ð13Þ

2.09.10 Ring Synthesis by Transformation of Another Ring No discussions on this reaction related to four-membered cyclic compounds with one selenium or tellurium atom were found in the literature for the period 1995–2005.

2.09.11 Synthesis of Particular Classes of Compounds The selenetanes that have been described in the literature have been constructed via three types of reactions. Selenetane derivatives are generally prepared via the [2þ2] two-component syntheses (Schemes 8 and 9; Equations 3–7). The [1þ3] two-component syntheses via the reaction of a selenium nucleophile with a three-carbon unit have been carried out (Scheme 6, and Equations 8–10, 12, and 13). One-component syntheses via rearrangementcyclization have also been performed (Scheme 7).

2.09.12 Important Compounds and Applications No discussions on this issue related to four-membered cyclic compounds with one selenium or tellurium atom were found in the literature for the period 1995–2005.

2.09.13 Further Developments Recently, generation of selenetane and telluretane has been reported. 2,6-Diselenaspiro[3.3]heptane and 2-thia-6selenaspiro[3.3]heptane have been prepared and were fully characterized by spectroscopic methods and by X-ray diffraction <2005IC77>. Formation of telluretane by the reaction of tellurium with 1-bromo-3-chloropropane in the system hydrazine hydrate-alkali has been confirmed <2006RJGC1970>. The prediction of the homolytic bond dissociation enthalpy (BDE) and adiabatic ionization potential (IP) of 4-hydroxy-2,2,3,5,6-pentamethylbenzoselenete and benzotelluretes has been calculated <2006OBC846>.

475

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Four-membered Rings with One Selenium or Tellurium Atom

References 1975BCJ2339 1981BCJ3701 1995CB1149 1995CC2461 1996CB1169 1996CHEC-II(1)823 1997CC525 1997OM3895 1998H633 1999JOC2694 1999PS429 2000CAR107 2001HCA1578 2001JA7166 2004CAR1787 2004H(62)521 2004IC5558 2005IC77 2006OBC846 2006RJGC1970

S. Kumakura and T. Kodama, Bull. Chem. Soc. Jpn., 1975, 48, 2339. S. Kumakura, Bull. Chem. Soc. Jpn., 1981, 54, 3701. H. Fischer, K. Treier, and C. Troll, Chem. Ber., 1995, 128, 1149. H. Fischer, K. Treier, C. Troll, and R. Stumpf, J. Chem. Soc., Chem. Commun., 1995, 2461. H. Fischer, C. Kalbas, and R. Stumpf, Chem. Ber., 1996, 129, 1169. M. R. Detty, in ‘Comprehensive Heterocyclic Chemistry II’, A. Padwa, Ed.; Elsevier, Oxford, UK, 1996, vol. 1B, p. 823. R. D. Adams and K. T. McBride, Chem. Commun., 1997, 525. R. D. Adams, K. T. McBride, and R. D. Rogers, Organometallics, 1997, 16, 3895. K. Takemura, K. Sakano, A. Takahashi, T. Sakamaki, and O. Mitsunobu, Heterocycles, 1998, 47, 633. A. A. L. Gunatilaka, F. D. Ramdayal, M. H. Sarragiotto, D. G. I. Kingston, D. L. Sackett, and E. Hamel, J. Org. Chem., 1999, 64, 2694. O. Schulze and J. Voss, Phosphorus, Sulfur Silicon Relat. Elem., 1999, 153–154, 429. G. Adiwidjaja, O. Schulze, J. Voss, and J. Wirsching, Carbohydr. Res., 2000, 325, 107. Z.-X. Wang and P. v. R. Schleyer, Helv. Chim. Acta, 2001, 84, 1578. K. Okuma, A. Okada, Y. Koga, and Y. Yokomori, J. Am. Chem. Soc., 2001, 123, 7166. O. Schulze, J. Voss, G. Adiwidjaja, and F. Olbrich, Carbohydr. Res., 2004, 339, 1787. P. K. Atanassov, A. Linden, and H. Heimgartner, Heterocycles, 2004, 62, 521. E. V. Dikarev, R. V. Shpanchenko, K. W. Andreini, E. Block, J. Jin, and M. A. Petrukhina, Inorg. Chem., 2004, 43, 5558. M. A. Petrukhina, C. Henck, B. Li, E. Block, J. Jin, S.-Z. Zhang, and R. Clerac, Inorg. Chem., 2005, 44, 77. D. Shanks, H. Frisell, H. Ottosson, and L. Engman, Org. Biomol. Chem., 2006, 4, 846. E. P. Levanova, A. V. Elaev, L. V. Klyba, E. R. Zhanchipova, V. A. Grabel’nykh, E. N. Sukhomazova, A. I. Albanov, N. V. Russavskaya, and N. A. Korchevin, Russ. J. Gen. Chem., 2006, 76, 1970.

Four-membered Rings with One Selenium or Tellurium Atom

Biographical Sketch

Mamoru Koketsu received his Ph.D. in 1995 at the Graduate School of Bioresources, Mie University. In 1997 he moved to his current position at Faculty of Engineering, Gifu University. In 2003 he became an associate professor in the Life Science Research Center, Gifu University. Within this period, he worked in the University of Iowa (Iowa, USA) as a visiting assistant professor (1999–2000).

Hideharu Ishihara graduated from the Faculty of Engineering, Gifu University in 1965, and continued his research as an assistant professor. He received his Ph.D. in 1979 at the Graduate School of Engineering, Tokyo Institute of Technology (Prof. Turuaki Mukaiyama). In 1991 he became a professor in the Faculty of Engineering, Gifu University. Within this period, he was chief of the Instrumental Analysis Center (1997–2001). He is Emeritus Professor, Gifu University.

477