Rhodium(I)-Catalyzed Bridged [5+2] Cycloaddition of cis-Allene-vinylcyclopropanes to Synthesize the Bicyclo[4.3.1]decane Skeleton

被引：56

作者：

Liu, Cheng-Hang ^{[1
]}

Yu, Zhi-Xiang ^{[1
]}

机构：

[1] Peking Univ, Coll Chem, Minist Educ, Key Lab Bioorgan Chem & Mol Engn,BNLMS, Beijing 100871, Peoples R China

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2017年 / 56卷 / 30期

关键词：

allenes; cycloaddition; density-functional calculations; rhodium; small ring compounds; CATALYZED INTERMOLECULAR 5+2; ASYMMETRIC TOTAL-SYNTHESIS; NATURAL-PRODUCT SYNTHESIS; DIELS-ALDER REACTION; ENE-VINYLCYCLOPROPANES; VINYL AZIRIDINES; 7-MEMBERED RINGS; ALKYNES; METAL; STEREOCHEMISTRY;

D O I：

10.1002/anie.201702288

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Previously reported was that cis-ene-vinylcyclopropanes (cis-ene-VCPs) underwent Rh-catalyzed [5+2] reaction to give 5,7-fused bicyclic products, where vinylcyclopropane (VCP) acts as five-carbon synthon. Unfortunately, this reaction had very limited scope. Replacing the 2 pi component of cis-ene-VCPs to allene moiety, the corresponding cis-allene-VCPs did not undergo the expected normal [5+2] cycloaddition to give 5,7-fused bicyclic products. Instead, the challenging bicyclo[ 4.3.1]decane skeleton was obtained via an unprecedented bridged [5+2] cycloaddition. DFT calculations were applied to understand why this bridged [5+2] reaction is favored over the anticipated but not realized normal [5+2] reaction.

引用

页码：8667 / 8671

页数：5

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