Synthesis of chiral quaternary fluorinated cyclic sulfamidates via palladium-catalyzed arylation with arylboronic acids

Journal Pre-proofs Synthesis of Chiral Quaternary Fluorinated Cyclic Sulfamidates via Palladiumcatalyzed Arylation with Arylboronic Acids Mu-Wang Chen, Xuechun Mao, Yue Ji, Jianjun Yuan, Zhihong Deng, Yiyuan Peng PII: DOI: Reference:

S0040-4039(19)31060-3 https://doi.org/10.1016/j.tetlet.2019.151280 TETL 151280

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Tetrahedron Letters

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30 August 2019 10 October 2019 12 October 2019

Please cite this article as: Chen, M-W., Mao, X., Ji, Y., Yuan, J., Deng, Z., Peng, Y., Synthesis of Chiral Quaternary Fluorinated Cyclic Sulfamidates via Palladium-catalyzed Arylation with Arylboronic Acids, Tetrahedron Letters (2019), doi: https://doi.org/10.1016/j.tetlet.2019.151280

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Synthesis of Chiral Quaternary Fluorinated Cyclic Sulfamidates via Palladium-catalyzed Arylation with Arylboronic Acids

Mu-Wang Chena, Xuechun Maoa, Yue Jib, Jianjun Yuana, Zhihong Denga, Yiyuan Peng*a O Ar'

O S O + ArB(OH)2 N

Rf 1

2

Pd(OCOCF3)2/(S)-tBu-Phox TFE, 40 oC

O Ar'

O S O NH

Rf Ar 3 up to 99% ee

O

t

N PPh2 (S)-tBu-Phox

Bu

1

Tetrahedron Letters journal homepage: www.elsevier.com

Synthesis of Chiral Quaternary Fluorinated Cyclic Sulfamidates via Palladiumcatalyzed Arylation with Arylboronic Acids Mu-Wang Chena, Xuechun Maoa, Yue Jib, Jianjun Yuana, Zhihong Denga, Yiyuan Peng*a Key Laboratory of Functional Small Organic Molecules, Ministry of Education, Jiangxi Province’s Key Laboratory of Green Chemistry, and Jiangxi Normal University, Nanchang 330022, China b College of Chemistry & Chemical Engineering, Xian Shiyou University, Xian 710065, China a

ARTICLE INFO

ABSTRACT

Article history: Received Received in revised form Accepted Available online

An enantioselective palladium-catalyzed arylation of fluorinated cyclic N-sulfonyl ketimines with arylboronic acids is described. This methodology provides an efficient and convenient route to chiral quaternary fluorinated cyclic sulfamidates in high yields with up to 99% ee. 2015 Elsevier Ltd. All rights reserved.

Keywords: asymmetric-addition quaternary fluorinated cyclic sulfamidate palladium catalyst arylboronic acid

Chiral cyclic sulfamidates are valuable and prevalent building blocks in biologically active natural products, agrochemicals, pharmacophores and functional materials (Figure 1).1 Therefore, their catalytic enantioselective syntheses have attracted a great deal of interests in the past decades. One of the most straightforward and atom-efficient approaches for the synthesis of chiral sulfamidates was asymmetric hydrogenation of cyclic sulfamidate ketimines.2-3 Another effect method to construction of chiral cyclic sulfamidates was through enzymes catalyzed intramolecular C-H amination.4 Furthermore, metal-catalyzed enantioselective addition of carbon nucleophiles (the organoboron reagents) to cyclic N-sulfonyl ketimines was proved to be a powerful strategy for synthesis of chiral cyclic sulfamidates (Scheme 1).5-13 Since the pioneering researches reported by Hayashi,6 Lam,7 Xu8 and Zhang9 et al10 the rhodium or palladium-catalyzed asymmetric addition of organoboron reagents to cyclic sulfamidates have been extensively studied. In addition, other transition-metal (Ni,11 Co,12 Ag13)-catalyzed asymmetric addition of nucleophiles to cyclic N-sulfonyl ketimines for the synthesis of chiral cyclic sulfamidates was also successively developed. In contrast, only a few methods8a,9a,10a have been applied to synthesis of chiral sulfamidates bearing a trifluoromethyl group on the quaternary carbon stereogenic center. Especially, the introduction of fluorine into organic molecules can greatly modify the lipophilicity, metabolic stability and biological activity of fluorinated compounds.14 In O O S N Me *

F3C

Ph

Inhibitor of HIV-1

O

O O S Et N

O

H N

O

O H Ph

Inhibitor of Calpain 1

Figure 1 Some bioactive molecules containing the chiral sulfamidates moiety

2013, Xu and co-workers reported a Rh-catalyzed asymmetric addition of arylboronic acids to trifluoromethyl cyclic N-sulfonyl ketimines, giving the trifluoromethylated sulfamidates with excellent enantioselectivity.8a Subsequently, a new approach based on palladium-catalyzed enantioselective addition of arylboronic acids to cyclic ketimines was described by Zhang’s group, which includes only one example of chiral trifluoromethylated sulfamidates with 95% ee and 71% yield under 10 mol% catalyst loading.9a Therefore, it is still necessary to develop efficient methods for the asymmetric synthesis of fluorinated cyclic sulfamidates in organic chemistry. Previous work: Metal-catalyzed asymmetric arylation of cyclic sulfamidate imines O O S N

+

ArB(OH)2

R

[M]/L* catalyst

O O S NH 

M = Rh, Pd, Ni, Co, Ag

Ar

R

R = H, alkyl, aryl, CO2R', CF3 This work: Pd-catalyzed asymmetric arylation of fluorinated cyclic sulfamidate imines O

Rf

O S O + N

ArB(OH)2

[Pd]/L* catalyst

O

O S O NH

Rf Ar 14 examples, up to 99% ee

Scheme 1. Catalytic asymmetric addition of arylboron reagents to cyclic sulfamidate imines. In the past decades, chiral palladium catalyst has been successfully applied in organic synthesis.2a,15 Especially, the pioneering work of the Pd-catalyzed asymmetric addition of arylboronic acids to aldimines was reported by Lu and coworkers.16 In 2013, an elegant work about the palladiumcatalyzed addition of arylboron acids to ketimines was first reported by Zhang.9 Subsequently, Lu/Hayashi 6e,17 and Zhou18 et al groups have also reported the related studies. Although great

Tetrahedron Letters

2

progress has been made in this area, achieving stereocontrol with a broad substrate scope is still highly desirable. Herein, we report a catalytic asymmetric arylation of fluorinated cyclic Nsulfonyl ketimines by chiral palladium complex, giving the chiral quaternary fluorinated cyclic sulfamidates in high yields with up to 99% ee.. We began our investigation on the addition of phenyl-boronic acid to 4-(trifluoromethyl)benzo[e][1,2,3]oxathiazine 2,2-dioxide 1a using Pd(OCOCF3)2/(R)-tBu-Phox as catalyst in trifluoroethanol (TFE) at 40 oC. Gratifyingly, the reaction proceeded smoothly and furnished 3a in 73% conversion and 99% ee (Table 1, entry 1). Subsequently, different solvents were examined, and solvent effect played a crucial role in both reactivity and enantioselectivity. The reaction shut down in dichloromethane, methanol or toluene (entries 2–4). Next, we further screened several commercially available chiral phosphine ligands (entries 5-7), L2 gave the desired product with excellent ee value and moderate yield. The planarly chiral ferrocene N-P ligand (L3) and axiallly chiral ligand Quinap (L4) afforded the desired product in excellent ee value but only moderate reactivity. Considering that 1a could not be completely converted into 3a and the formation of boronic acid self-coupling products, we tried to add phenylboronic acid step by step. To our delight, the conversion was further improved, and enantioselectivity was also retained with another 1.5 equivalent 2a was added after 24 hours. Therefore, the optimal conditions were established: Pd(OCOCF3)2/(S)-tBu-Phox as the catalyst, TFE as solvent under 40 oC and stage addition of arylboronic acid.

investigated the different electronic properties of substituent on the aromatic ring. The electronic properties of substrates had a little effect on reactivity and enantioselectivity (3d-3f). In addition, 1g can proceed smoothly with excellent yield and enantioselectivity by increasing the catalyst loading to 8%. In addition, a variety of arylboronic acids were examined for addition to different fluorinated cyclic N-sulfonyl ketimines (1h1n). The electronic properties of the arylboronic acids had a certain influence on reactivity (3j-3l). For examples, electron-rich arylboronic acids (2j & 2k) both gave excellent yields, but arylboronic acids bearing electron-withdrawing group such as Cl gave moderate yield (3l, 61%). Notably, 3,5-dimethylboronic acid (2n) also gave excellent yield and enantioselectivity. Unfortunately, only <5 % conversion was observed for the reaction using o-tolylboronic acid under optimized conditions. and no product was observed for the reaction using alkenylboronic or alkylboronic acid. Scheme 2. Palladium-catalyzed asymmetric addition of arylboronic acids 2 to fluorinated cyclic sulfonyl ketimines 1a O Ar'

O S O + N

Pd(OCOCF3)2/L*

PhB(OH)2



Solvent, 40 oC

CF3

F3C

1a

2a

Entry

L

TFE

1

Conv. (%)b

L1

73

O

Me

Ee (%)c

Me

CH2Cl2

L1

NR

NA

3

MeOH

L1

NR

NA

4

Toluene

L1

NR

NA

5

TFE

L2

55

99

6

TFE

L3

35

99

7

TFE

L4

20

98

8

TFE

L1

>95

99

O

O

t

N PPh2 L1

Bu

O F3C

t

N PPh2 L2

t

Bu

OMe 3j >99% ee, 92% yield O

L3

3mb,c >99% ee, 88% yield

PPh2

PPh2

Fe

L4

Reaction conditions: Pd(OCOCF3)2 (4.0 mol%), L (6.0 mol%), 1a (0.10 mmol), 2a (0.15 mmol), Solvent (2.0 mL), 40 oC, 72 h. b Determined by 1H NMR. c Determined by HPLC. d 1.5 equivalent 2a was added after 24 hours. NR: no reaction, NA: no analysis. a

With the optimized conditions in hand, we next explored the substrate scope of the addition reaction (Scheme 2). Various substrates performed very well under the standard reaction conditions with excellent enantioselectivities (99%) and high yields (61–99%). For different fluoroalkyl-substituted cyclic Nsulfonyl ketimines 1b and 1c, both of them provided the desired products with >99% ee and good yields. Subsequently, we

F3C Ph 3f >99% ee, 78% yield

O S O NH

O

Me

O S O NH

F3C

O

OMe 3i >99% ee, 71% yield

O S O NH

Me

O S O NH

O

F3C

Me 3kb >99% ee, 95% yield Me

O S O NH

O S O NH

O

Cl

F3C

N

N

Bu

Me

F3C

Me

O S O NH

Me 3h >99% ee, 77% yield

O S O NH

O S O NH

F3CF2C Ph 3c >99% ee, 86% yield

F3C

F3C O

O

O S O NH

3gb,c >99% ee, 92% yield

Me

O

F3C Ph 3e >99% ee, 93% yield

F3C

99

O

MeO

F3C Ph 3d >99% ee, 99% yield O

O S O NH

HF2C Ph 3b >99% ee, 98% yield

O S O NH

O S O NH

Rf Ar 3 O

F3C Ph 3a >99% ee, 81% yield

Ph

2

d

TFE, 40 oC

O S O NH

O

3a

Solvent

Ar'

2

1

O S O NH

O

O

Pd(OCOCF3)2/(S)-tBu-Phox

Rf

Table 1 Optimization of reaction parametersa O

O S O + ArB(OH)2 N

O

O S O NH

F3C

Cl 3lb >99% ee, 61% yield

O Me

O S O NH

F3C R Me 3nb >99% ee, 99% yield

R = alkenyl, alkyl NR

Reaction conditions: Pd(OCOCF3)2 (4.0 mol%), (S)-tBu-Phox (6.0 mol%), 1 (0.20 mmol), 2 (0.60 mmol)(stage addition: first addition 1.5 equivalent 2 and then another 1.5 equivalent 2 was added after 24 hours ), TFE (3.0 mL), 40 oC, 72 h, the ee values determined by HPLC. b 80 oC. c Pd(OCOCF3)2 (8.0 mol%), (S)-tBu-Phox (12.0 mol%). NR = no reaction. a

Based on the above results, the stereochemistry of this reaction could be explained by the stereochemical models in Figure 2. The fluorinated cyclic N-sulfonyl imine bound to Pd center is in trans to the ligand’s diphenylphosphine group, and aryl group from the boronic acid is in cis to diphenylphosphine group.9b There are two possible orientations in the transition state,

3 but due to the steric interaction between the sulfonyl moiety of the ketimine substrate and the bulky tertiary butyl group of ligand, one leads to the disfavored configuration, and the other orientation does not suffer from such interactions, leading to the R product, which is the major enantiomer obtained in experiment. 6. O Ph2P F3C Ar

H

N

Pd

t

N

Bu

O

S O O A: Disfavored

O H O N Ot Bu O S Ph2P Pd N Ar CF3

7.

B: Favored

8. O

F3C

O S O NH Ar

Minor enantiomer

O

F3C

O S O NH Ar

Major enantiomer

9.

Figure 2. Stereochemical model In summary, we have developed a highly enantioselective palladium-catalyzed arylation of fluorinated cyclic N-sulfonyl ketimines with arylboronic acids. This methodology provides an efficient and facile route to chiral quaternary fluorinated cyclic sulfamidates in high yields with up to 99% ee. Further investigations on asymmetric addition of nucleophile to fluorinated cyclic N-sulfonyl ketimines are currently on going in our laboratory.

10.

11.

Acknowledgments We are grateful for financial support from the National Natural Science Foundation of China (21502188, 21801204 21362014 and 21762020), the Science and Technology Program of Xian, China (201805038YD16CG22(4)).

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Tetrahedron Letters

Dear Editor Prof. Lin, Enclosed please find our manuscript entitled “Synthesis of Chiral Quaternary Fluorinated Cyclic Sulfamidates via Palladium-catalyzed Arylation with Arylboronic Acids” Following is the highlights for publication as an article in Tetrahedron Letters. (1) Arylation of fluorinated cyclic ketimines with arylboronic acids was reported. (2) The substrate scope is good and the catalyst loading is relatively low. (3) Chiral fluorinated cyclic sulfamidates was synthesized with up to 99% ee. 19.