Rh-Catalyzed C-C Cleavage of Benzyl/Allylic Alcohols to Produce   Benzyl/Allylic Amines or other Alcohols by Nucleophilic Addition of   Intermediate Rhodacycles to Aldehydes and Imines

doi:10.1002/chem.201201867

CORC > 北京大学 > 化学与分子工程学院

	Rh-Catalyzed C-C Cleavage of Benzyl/Allylic Alcohols to Produce Benzyl/Allylic Amines or other Alcohols by Nucleophilic Addition of Intermediate Rhodacycles to Aldehydes and Imines
	Zhang, Xi-Sha ; Li, Yang ; Li, Hu ; Chen, Kang ; Lei, Zhi-Quan ; Shi, Zhang-Jie
刊名	chemistry a european journal
	2012
关键词	allylic compounds C-C activation rhodium alcohols synthetic methods CARBON-CARBON BOND QUATERNARY STEREOGENIC CENTERS H BOND ARYLBORONIC ACIDS INTERNAL ALKYNES ORTHOPLATINATED TRIARYLPHOSPHITE ENANTIOSELECTIVE SYNTHESIS DIRECT FUNCTIONALIZATION ASYMMETRIC CONSTRUCTION OXIDATIVE OLEFINATION
DOI	10.1002/chem.201201867
英文摘要	We report three transformations: 1) direct transformation from biarylmethanols into biarylmethylamines; 2) direct transformation from one biarylmethanol into another biarylmethanol; 3) direct transformation from allylic alcohols into allylic amines. These transformations are based on pyridyl-directed Rh-catalyzed C?C bond cleavage of secondary alcohols and subsequent addition to C?X (X=N or O) double bonds. The reaction conditions are simple and no additive is required. The driving force of C?C bond cleavage is the formation of the stable rhodacycle intermediate. Other directing groups, such as the pyrazolyl group, can also be used although it is not as efficient as the pyridyl group. We carried out in-depth investigations for transformation 1 and found that: 1) the substrate scope was broad and electron-rich alcohols and electron-deficient imines are more efficient; 2) as the leaving group, aldehyde had no significant impact on either the C?C bond cleavage or the whole transformation; 3) mechanistic studies (intermediate isolation, in situ NMR spectroscopic studies, competing reactions, isotopic labeling experiments) implied that: i) The C?C cleavage was very efficient under these conditions; ii) there is an equilibrium between the rhodacycle intermediate and the protonated byproduct phenylpyridine; iii) the addition step of the rhodacycle intermediate to imines was slower than the C?C cleavage and the equilibrium between the rhodacycle and phenylpyridine; iv) the whole transformation was a combination of two sequences of C?C cleavage/nucleophilic addition and C?C cleavage/protonation/C?H activation/nucleophilic addition, with the latter being perhaps the main pathway. We also demonstrated the first example of cleavage of an C(alkenyl)?C(benzyl) bond. These transformations showed the exchange (or substitution) of the alcohol group with either an amine or another alcohol group. Like the group transplant, this method offers a new concept that can be used to directly synthesize the desired products from other chemicals through reorganization of carbon skeletons.; http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000312163500038&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=8e1609b174ce4e31116a60747a720701 ; Chemistry, Multidisciplinary; SCI(E); PubMed; 21; REVIEW; 50; 16214-16225; 18
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/191926]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Zhang, Xi-Sha,Li, Yang,Li, Hu,et al. Rh-Catalyzed C-C Cleavage of Benzyl/Allylic Alcohols to Produce Benzyl/Allylic Amines or other Alcohols by Nucleophilic Addition of Intermediate Rhodacycles to Aldehydes and Imines[J]. chemistry a european journal,2012.
APA	Zhang, Xi-Sha,Li, Yang,Li, Hu,Chen, Kang,Lei, Zhi-Quan,&Shi, Zhang-Jie.(2012).Rh-Catalyzed C-C Cleavage of Benzyl/Allylic Alcohols to Produce Benzyl/Allylic Amines or other Alcohols by Nucleophilic Addition of Intermediate Rhodacycles to Aldehydes and Imines.chemistry a european journal.
MLA	Zhang, Xi-Sha,et al."Rh-Catalyzed C-C Cleavage of Benzyl/Allylic Alcohols to Produce Benzyl/Allylic Amines or other Alcohols by Nucleophilic Addition of Intermediate Rhodacycles to Aldehydes and Imines".chemistry a european journal (2012).