A Comparison of Me2(CH2Cl)SiCN and Me3SiCN in Catalytic Enantioselective Cyanation of Aldehydes

doi:10.6023/A16100541

Acta Chim. Sinica ›› 2016, Vol. 74 ›› Issue (12): 984-989.DOI: 10.6023/A16100541 Previous Articles Next Articles

Special Issue: 聚集诱导发光

Communication

Me₂(CH₂Cl)SiCN和Me₃SiCN在醛的不对称氰化反应中的比较研究

叶旭^a, 曾兴平^a, 周剑^a,b

a 华东师范大学化学与分子工程学院绿色化学与化工过程绿色化上海市重点实验室上海 200062;
b 中国科学院上海有机化学研究所金属有机化学国家重点实验室上海 200032

投稿日期:2016-10-12 发布日期:2016-12-20
通讯作者: 曾兴平, 周剑 E-mail:jzhou@chem.ecnu.edu.cn;zengxingping2004@163.com
基金资助:
项目受国家自然科学基金（No.21472049）资助.

A Comparison of Me₂(CH₂Cl)SiCN and Me₃SiCN in Catalytic Enantioselective Cyanation of Aldehydes

Ye Xu^a, Zeng Xingping^a, Zhou Jian^a,b

a Shanghai Key Laboratory of Green Chemistry and Chemical Processes, School of Chemistry and Molecular Engineering, East China Normal University, Shanghai 200062;
b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, CAS, Shanghai 200032, China

Received:2016-10-12 Published:2016-12-20
Supported by:
Project supported by the National Natural Science Foundation of China (No. 21472049).

1. A Comparison of Me₂(CH₂Cl)SiCN and Me₃SiCN in Catalytic Enantioselective Cyanation of Aldehydes.PDF(6334KB)

Abstract

We report the comparative studies of Me₂(CH₂Cl) SiCN and Me₃SiCN in the catalytic enantioselective cyanation reactions of aldehydes,which were catalyzed by the merger of 5 mol% Jacobsen's catalyst (salen) AlCl (R,R)-1 and 6 mol% ylide 2a,and are conducted at -50℃ using i-Pr2O as the solvent.This was based on our recent finding that (R,R)-1 could be effectively activated by ylide to form an enhanced chiral Lewis acid.Generally,the use of Me₂(CH₂Cl) SiCN as the cyanating reagent afforded obviously higher activity in the reaction of all the aldehydes we examined,along with by-and-large similar enantioselectivity.This further suggested that Me₂(CH₂Cl) SiCN might be useful cyanating reagent to develop reaction involving the use of less active substrates.Under the indicated condition,aromatic aldehydes worked well to give the desired adducts in up to 99% yield and 94% ee,but the reactions of vinyl aldehydes and aliphatic aldehydes were not successful.All the reactions were performed by the following general procedure.To a 4 mL vial were successively added complex (R,R)-1(30.3 mg,0.05 mmol),ylide 2a (22.6 mg,0.06 mmol) and i-Pr₂O (1.0 mL).The resulting solution was stirred at -50℃ for 0.5 h before the addition of aldehydes (1.0 mmol) and the cyanating reagent,Me₂(CH₂Cl) SiCN or Me₃SiCN (250 μL,2.0 mmol).After TLC analysis indicated the full consumption of the aldehydes,the reaction mixture was filtrated with a pad of silica gel and eluted with Et₂O.The filtrate is concentrated under reduced pressure to give a crude residue for column chromatography purification.In contrast,when Me₂(CH₂Cl) SiCN is used,both cyanohydrins and its silyl ethers were obtained,so a further deprotection by p-TsOH is adopted to obtain free cyanohydrins as the only product.

Key words: enantioselective cyanation, TMSCN, Me₂(CH₂Cl) SiCN, (Salen) AlCl/ylide complex, chiral cyanohydrins

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Ye Xu, Zeng Xingping, Zhou Jian. A Comparison of Me₂(CH₂Cl)SiCN and Me₃SiCN in Catalytic Enantioselective Cyanation of Aldehydes[J]. Acta Chim. Sinica, 2016, 74(12): 984-989.

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[19] We tried the one-pot sequential asymmetric cyanosilylation/chloromethyl transfer reaction, and the corresponding aromatic methyl ketones were obtained as the major product. For the proposed mechanism, see supporting information:???A16100541-1???
[20] According to the reviewer's suggestion, we investigated the effect of Ph3PO, which could generate from side Wittig reaction, on the cyanation of p-chlorobenzaldehyde and TMSCN. NMR analysis of the crude reaction mixture showed the signals of both Ph3PO and ylide, suggesting ylide 2a was not consumed at the end of the cyanation. The addition of 6 mol% of Ph3PO did not appreciably accelerate the cyanation reaction. When Ph3PO and (salen)AlCl were used as the catalysts, in the absence of ylide 2a, the reaction could also proceed well, albeit in a lower reaction rate (finish within 2 days and afford 91% ee). This suggested that the Ph3PO produced from side Wittig reaction had little acceleration effect on the reactivity, but slightly decreased the enantioselectivity of the reaction. (Cheng, B.)???A16100541-2???

Me₂(CH₂Cl)SiCN和Me₃SiCN在醛的不对称氰化反应中的比较研究

A Comparison of Me₂(CH₂Cl)SiCN and Me₃SiCN in Catalytic Enantioselective Cyanation of Aldehydes

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Me2(CH2Cl)SiCN和Me3SiCN在醛的不对称氰化反应中的比较研究