Asymmetric aminocarbonylation of iodoalkenes in the presence of α-phenylethylamine as an N-nucleophile

Q2 Chemistry Tetrahedron, asymmetry Pub Date : 2017-12-15 DOI:10.1016/j.tetasy.2017.10.012

Gábor Mikle , Borbála Boros , László Kollár

{"title":"Asymmetric aminocarbonylation of iodoalkenes in the presence of α-phenylethylamine as an N-nucleophile","authors":"Gábor Mikle , Borbála Boros , László Kollár","doi":"10.1016/j.tetasy.2017.10.012","DOIUrl":null,"url":null,"abstract":"<div>Iodoalkenes, such as 2-iodo-bornene, 17-iodoandrost-16-ene, 3-methoxy-17-iodoestra-1,3,5(10),16-ene, 3β-hydroxy-20-iodopregna-5,20-diene and 3β-hydroxy-12-iodo-5α,25R-spirost-11-ene were aminocarbonylated with enantiomerically pure and racemic α-phenylethylamine as the N-nucleophile in the presence of palladium(0) catalysts. Monodentate and bidentate (chiral and achiral) phosphines were used as ligands in the catalytic system. All diastereoisomers of the corresponding carboxamides were characterised as pure stereoisomers using both α-phenylethylamine and iodoalkene in enantiomerically pure form. The diastereoisomers were obtained in moderate to high yields in a chemoselective reaction, i.e., carboxamides due to single carbon monoxide insertion were formed exclusively, with no double CO insertion leading to 2-ketocarboxamides. Diastereoselectivities of the aminocarbonylation were investigated using the N-nucleophile in racemic form by the systematic variation of the catalyst.</div>","PeriodicalId":22237,"journal":{"name":"Tetrahedron, asymmetry","volume":null,"pages":null},"PeriodicalIF":0.0000,"publicationDate":"2017-12-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://sci-hub-pdf.com/10.1016/j.tetasy.2017.10.012","citationCount":"9","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Tetrahedron, asymmetry","FirstCategoryId":"1085","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S0957416617303993","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"Chemistry","Score":null,"Total":0}

引用次数: 9

Abstract

Iodoalkenes, such as 2-iodo-bornene, 17-iodoandrost-16-ene, 3-methoxy-17-iodoestra-1,3,5(10),16-ene, 3β-hydroxy-20-iodopregna-5,20-diene and 3β-hydroxy-12-iodo-5α,25R-spirost-11-ene were aminocarbonylated with enantiomerically pure and racemic α-phenylethylamine as the N-nucleophile in the presence of palladium(0) catalysts. Monodentate and bidentate (chiral and achiral) phosphines were used as ligands in the catalytic system. All diastereoisomers of the corresponding carboxamides were characterised as pure stereoisomers using both α-phenylethylamine and iodoalkene in enantiomerically pure form. The diastereoisomers were obtained in moderate to high yields in a chemoselective reaction, i.e., carboxamides due to single carbon monoxide insertion were formed exclusively, with no double CO insertion leading to 2-ketocarboxamides. Diastereoselectivities of the aminocarbonylation were investigated using the N-nucleophile in racemic form by the systematic variation of the catalyst.

Abstract Image

查看原文

微信好友朋友圈 QQ好友复制链接

本刊更多论文

α-苯乙胺作为n亲核试剂存在下碘烯烃的不对称氨基羰基化反应

在钯(0)催化剂的作用下，以对映体纯外消旋α-苯乙胺为n -亲核试剂进行了2-碘龙骨烯、17-碘雄酮-16-烯、3-甲氧基-17-碘酮-1,3,5(10)、16-烯、3- β-羟基-20-碘孕烯-5,20-二烯和3- β-羟基-12-碘-5α， 25r -螺-11-烯等碘烯烃的氨基羰基化反应。单齿和双齿(手性和非手性)膦作为配体用于催化体系。在α-苯乙胺和碘烯的对映体纯形式下，相应的羧胺的所有非对映异构体都被表征为纯立体异构体。这些非对映异构体是通过化学选择性反应以中高收率获得的，即由于单一氧化碳插入而形成的羧胺，没有双一氧化碳插入导致2-酮羧胺。通过催化剂的系统变化，研究了外消旋形式的n -亲核试剂对氨基羰基化反应的非对映选择性。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

求助全文

约1分钟内获得全文去求助

来源期刊

Tetrahedron, asymmetry 化学-无机化学与核化学

CiteScore

4.70

自引率

0.00%

发文量

审稿时长

1 months

期刊介绍： Cessation. Tetrahedron: Asymmetry presents experimental or theoretical research results of outstanding significance and timeliness on asymmetry in organic, inorganic, organometallic and physical chemistry, as well as its application to related disciplines, especially bio-organic chemistry. The journal publishes critical reviews, original research articles and preliminary communications dealing with all aspects of the chemical, physical and theoretical properties of non-racemic organic and inorganic materials and processes. Topics relevant to the journal include: the physico-chemical and biological properties of enantiomers; strategies and methodologies of asymmetric synthesis; resolution; chirality recognition and enhancement; analytical techniques for assessing enantiomeric purity and the unambiguous determination of absolute configuration; and molecular graphics and modelling methods for interpreting and predicting asymmetric phenomena. Papers describing the synthesis or properties of non-racemic molecules will be required to include a separate statement in the form of a Stereochemistry Abstract, for publication in the same issue, of the criteria used for the assignment of configuration and enantiomeric purity.

期刊最新文献

Graphical contents list Editorial board Contributors to this issue Nucleophilic substitution at phosphorus: stereochemistry and mechanisms Enantioselective synthesis of chiral 4H-pyran derivatives through [3+3] tandem reaction over a squaramide catalyst