SIOC OpenIR  > 金属有机化学国家重点实验室
cis-beta-Bis(carbonyl) Ruthenium-Salen Complexes: X-ray Crystal Structures and Remarkable Catalytic Properties toward Asymmetric Intramolecular Alkene Cyclopropanation
其他题名cis-beta-Bis(carbonyl) Ruthenium-Salen Complexes: X-ray Crystal Structures and Remarkable Catalytic Properties toward Asymmetric Intramolecular Alkene Cyclopropanation
Xu ZJ(徐镇江); Fang R(方然); Zhao CY(赵存元); Huang JS(黄杰生); Li GY(李功勇); Zhu NY(朱年永); Zhi ZM(支志明)
2009
发表期刊J. Am. Chem. Soc.
ISSN0002-7863
卷号131期号:12页码:4405-4417
摘要cis-beta-[Ru-II(salen(A))(CO)(2)] (salen(A) = N,N'-bis(3-R-1-5-R-2-salicylidene)-1,2-cyclohexenediamine dianion; R-1 = R-2 = Bu-1, 1a; R-1 = Pr-i, R-2 = H, 1b; R-1 = Bu-1, R-2 = H, 1c) complexes were prepared by treating Ru-3(CO)(12) with the respective H(2)salen(A) in 1,2,4-trichlorobenzene and structurally characterized by X-ray crystallography. Complexes 1a-c catalyze intramolecular cyclopropanation of trans-allylic diazoacetates N2CHCO2CH2CH=CHR (3, R = Ph, 4-CIC6H4, 4-BrC6H4, 4-MeC6H4, 4-MeOC6H4, 2-MeC6H4, 2-furanyl) under light irradiation to give cyclopropyl lactones 4 in up to 96% yield and up to 98% ee. DFT calculations on intramolecular cyclopropanation of 3a (R = Ph) with model catalyst cis-beta-[Ru-II(salen(A0)) (CO)(2)] (salen(A0) = N,N'-bis(salicylidene)-1,2-cyclohexenediamine dianion) reveal the intermediacy of both cis-beta- and trans[Ru(salen (A0))(CHCO2CH2CH=CHPh)(CO)] bearing salen(A0) in a nonplanar and planar coordination mode, respectively, with the cis-beta-carbene species being a major intermediate in the catalytic carbenoid transfer reaction. The intramolecular cyclopropanation from the cis-beta-carbene species is the most favorable pathway and features an early transition state and an asynchronous concerted [2 + 1) addition mechanism. Enantioselectivities in the reactions involving [Ru(salen(A0))(CHCO2CH2CH=CHPh)(CO)] were predicted to be 77% ee for the trans-carbene species and 96% ee for the cis-beta-carbene species; the former dramatically increases to 98% ee, whereas the latter slightly increases to 99% ee, upon replacing salen(A0) with salen(A1) (RI = R 2 = B). The observed variation in enantioselectivity (90-98% ee) for the conversion of 3a to 4a catalyzed by 1a-c could result from an equilibrium between cis-beta (major) and trans (minor) ruthenium-carbene intermediates.
学科领域金属有机化学
部门归属上海有机所; 香港大学
URL查看原文
收录类别SCI
语种英语
WOS记录号WOS:000264792900051
引用统计
文献类型期刊论文
条目标识符http://ir.sioc.ac.cn/handle/331003/27873
专题金属有机化学国家重点实验室
通讯作者Zhi ZM(支志明)
推荐引用方式
GB/T 7714
Xu ZJ,Fang R,Zhao CY,et al. cis-beta-Bis(carbonyl) Ruthenium-Salen Complexes: X-ray Crystal Structures and Remarkable Catalytic Properties toward Asymmetric Intramolecular Alkene Cyclopropanation[J]. J. Am. Chem. Soc.,2009,131(12):4405-4417.
APA 徐镇江.,方然.,赵存元.,黄杰生.,李功勇.,...&支志明.(2009).cis-beta-Bis(carbonyl) Ruthenium-Salen Complexes: X-ray Crystal Structures and Remarkable Catalytic Properties toward Asymmetric Intramolecular Alkene Cyclopropanation.J. Am. Chem. Soc.,131(12),4405-4417.
MLA 徐镇江,et al."cis-beta-Bis(carbonyl) Ruthenium-Salen Complexes: X-ray Crystal Structures and Remarkable Catalytic Properties toward Asymmetric Intramolecular Alkene Cyclopropanation".J. Am. Chem. Soc. 131.12(2009):4405-4417.
条目包含的文件
文件名称/大小 文献类型 版本类型 开放类型 使用许可
2009345.pdf(1851KB) 开放获取--请求全文
个性服务
推荐该条目
保存到收藏夹
查看访问统计
导出为Endnote文件
谷歌学术
谷歌学术中相似的文章
[徐镇江]的文章
[方然]的文章
[赵存元]的文章
百度学术
百度学术中相似的文章
[徐镇江]的文章
[方然]的文章
[赵存元]的文章
必应学术
必应学术中相似的文章
[徐镇江]的文章
[方然]的文章
[赵存元]的文章
相关权益政策
暂无数据
收藏/分享
所有评论 (0)
暂无评论
 

除非特别说明,本系统中所有内容都受版权保护,并保留所有权利。