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烯硒化反应：相对反应活性、立体化学和不对称诱导的综合分析，以及与亚磺化反应的比较。

Alkene selenenylation: A comprehensive analysis of relative reactivities, stereochemistry and asymmetric induction, and their comparisons with sulfenylation.

机构信息

University of the Basque Country UPV/EHU, San Sebastian, Spain.

出版信息

Beilstein J Org Chem. 2011;7:744-58. doi: 10.3762/bjoc.7.85. Epub 2011 Jun 3.

DOI:10.3762/bjoc.7.85
PMID:21804870
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC3135076/
Abstract

A broad perspective of various factors influencing alkene selenenylation has been developed by concurrent detailed analysis of key experimental and theoretical data, such as asymmetric induction, stereochemistry, relative reactivities, and comparison with that of alkene sulfenylation. Alkyl group branching α to the double bond was shown to have the greatest effect on alkene reactivity and the stereochemical outcome of corresponding addition reactions. This is in sharp contrast with other additions to alkenes, which depend more on the degree of substitution on C=C or upon substituent electronic effects. Electronic and steric effects influencing asymmetric induction, stereochemistry, regiochemistry, and relative reactivities in the addition of PhSeOTf to alkenes are compared and contrasted with those of PhSCl.

摘要

通过对关键实验和理论数据（如不对称诱导、立体化学、相对反应活性以及与烯烃亚磺酰化的比较）的详细分析，我们对影响烯硒化的各种因素有了更广泛的了解。研究表明，与双键α位相连的烷基支链对烯烃的反应活性和相应加成反应的立体化学结果影响最大。这与其他烯烃加成反应形成鲜明对比，后者更多地取决于 C=C 的取代程度或取代基的电子效应。本文比较并对比了 PhSeOTf 与烯烃加成反应中影响不对称诱导、立体化学、区域化学和相对反应活性的电子和空间效应，以及 PhSCl 的影响。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fe33/3135076/f9fe4e0c9824/Beilstein_J_Org_Chem-07-744-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fe33/3135076/328aebc205eb/Beilstein_J_Org_Chem-07-744-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fe33/3135076/923764b6f175/Beilstein_J_Org_Chem-07-744-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fe33/3135076/89b9dada152b/Beilstein_J_Org_Chem-07-744-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fe33/3135076/caa43780a62c/Beilstein_J_Org_Chem-07-744-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fe33/3135076/04f0883aa2ce/Beilstein_J_Org_Chem-07-744-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fe33/3135076/09629753ab49/Beilstein_J_Org_Chem-07-744-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fe33/3135076/3ccba96be0bb/Beilstein_J_Org_Chem-07-744-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fe33/3135076/f9fe4e0c9824/Beilstein_J_Org_Chem-07-744-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fe33/3135076/328aebc205eb/Beilstein_J_Org_Chem-07-744-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fe33/3135076/923764b6f175/Beilstein_J_Org_Chem-07-744-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fe33/3135076/89b9dada152b/Beilstein_J_Org_Chem-07-744-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fe33/3135076/caa43780a62c/Beilstein_J_Org_Chem-07-744-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fe33/3135076/04f0883aa2ce/Beilstein_J_Org_Chem-07-744-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fe33/3135076/09629753ab49/Beilstein_J_Org_Chem-07-744-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fe33/3135076/3ccba96be0bb/Beilstein_J_Org_Chem-07-744-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/fe33/3135076/f9fe4e0c9824/Beilstein_J_Org_Chem-07-744-g007.jpg

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