Enantioselective intramolecular cyclopropanation of cis-alkenes by chiral ruthenium(II) Schiff base catalysts and crystal structures of (Schiff base)ruthenium complexes containing carbene, PPh3, and CO ligands

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	Enantioselective intramolecular cyclopropanation of cis-alkenes by chiral ruthenium(II) Schiff base catalysts and crystal structures of (Schiff base)ruthenium complexes containing carbene, PPh3, and CO ligands
	Li GY(李功勇) ; Zhang J(张静) ; Chen WX(陈伟雄) ; Xu ZJ(徐镇江) ; Zhu NY(朱年勇) ; Zhi ZM(支志明)
刊名	Organometallics
	2006
卷号	25 期号:7 页码:1676-1688
ISSN号	0276-7333
其他题名	手性钌席夫碱络合物结构及其催化的分子内环丙烷化反应的研究
通讯作者	支志明
英文摘要	The enantioselective intramolecular cyclopropanation of cis-substituted allylic diazoacetates catalyzed by the chiral ruthenium Schiff base complexes [RU(Schiff base)(PPh(3)h] (1) is described. Among this class of complexes examined, [Ru(2-Br-salen)(PPh3)(2)] (1a) is the most effective, catalyzing intramolecular cyclopropanation of cis-allylic diazoacetates cis-(CRH=CH)CH2OC(O)CHN2, (R = alkyl, aryl) in CHCl3 solution to give [3.1.0.]-bicyclic lactones with yields and ee values up to 71 and 90%, respectively. The analogous reactions of cis-alkenyl diazoacetates using [Ru(Schiff base)(CO)] (2) as catalyst gave comparable enantioselectivities (up to 91% ee) but lower product yields of 20-38%. Treatment of [Ru(2,4-X-salen)(PPh3)(2)] (1d, X = Br; 1e, X = Cl; 1f, X = 1) with N2C(p-YC6H4)(2) (Y = H, MeO) and N-methylimidazole (MeIm) or pyridine (py) gave the monocarbene complexes [Ru(2,4-X-salen)(C(pYC(6)H(4))(2))(MeIm)] (3a, X = Br, Y = H; 3b, X = Cl, Y = H; 3c, X = I, Y = H; 3d, X = Br, Y = OMe) and [Ru(2,4-Br-salen)(CPh2)(py)] (4, H-2(2,4-Br-salen) = bis(3,5-dibromosalicylidene)-(1R,2R)-cyclo-hexanediamine), respectively. X-ray crystal structure determinations revealed Ru=C(carbene) distances of 1.921(12) angstrom for 3a, 1.913(5) angstrom for 3b, 1.919(14) angstrom for 3c, 1.910(2) angstrom for 3d, and 1.917(4) angstrom for 4. A comparison of the structures and electrochemistry of 1, [Ru(Schiff base) (CO) (MeIm)], 3, and 4 with those of the porphyrin analogues is presented.
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/om051009i
语种	英语
WOS记录号	WOS:000236288100019
公开日期	2013-08-14
内容类型	期刊论文
源URL	[http://202.127.28.38/handle/331003/27645]
专题	上海有机化学研究所_上海有机化学研究所
推荐引用方式 GB/T 7714	Li GY,Zhang J,Chen WX,et al. Enantioselective intramolecular cyclopropanation of cis-alkenes by chiral ruthenium(II) Schiff base catalysts and crystal structures of (Schiff base)ruthenium complexes containing carbene, PPh3, and CO ligands[J]. Organometallics,2006,25(7):1676-1688.
APA	李功勇,张静,陈伟雄,徐镇江,朱年勇,&支志明.(2006).Enantioselective intramolecular cyclopropanation of cis-alkenes by chiral ruthenium(II) Schiff base catalysts and crystal structures of (Schiff base)ruthenium complexes containing carbene, PPh3, and CO ligands.Organometallics,25(7),1676-1688.
MLA	李功勇,et al."Enantioselective intramolecular cyclopropanation of cis-alkenes by chiral ruthenium(II) Schiff base catalysts and crystal structures of (Schiff base)ruthenium complexes containing carbene, PPh3, and CO ligands".Organometallics 25.7(2006):1676-1688.