cis-beta-Bis(carbonyl) Ruthenium-Salen Complexes: X-ray Crystal Structures and Remarkable Catalytic Properties toward Asymmetric Intramolecular Alkene Cyclopropanation

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	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)
刊名	J. Am. Chem. Soc.
	2009
卷号	131 期号:12 页码:4405-4417
ISSN号	0002-7863
其他题名	cis-beta-Bis(carbonyl) Ruthenium-Salen Complexes: X-ray Crystal Structures and Remarkable Catalytic Properties toward Asymmetric Intramolecular Alkene Cyclopropanation
通讯作者	支志明
英文摘要	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.
学科主题	金属有机化学
收录类别	SCI
原文出处	http://dx.doi.org/10.1021/ja8086399
语种	英语
WOS记录号	WOS:000264792900051
公开日期	2013-08-22
内容类型	期刊论文
源URL	[http://202.127.28.38/handle/331003/27873]
专题	上海有机化学研究所_金属有机化学国家重点实验室
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.