trans-RhCl(CO)(PPh3)(2)-catalyzed monomeric and dimeric cycloisomerization of propargylic 2,3-dienoates. Establishment of alpha,beta-unsaturated delta-lactone rings by cyclometallation

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	trans-RhCl(CO)(PPh3)(2)-catalyzed monomeric and dimeric cycloisomerization of propargylic 2,3-dienoates. Establishment of alpha,beta-unsaturated delta-lactone rings by cyclometallation
	Jiang XF(姜雪峰) ; Ma SM(麻生明)
刊名	J. Am. Chem. Soc.
	2007
卷号	129 期号:37 页码:11600-11607
ISSN号	0002-7863
其他题名	trans-RhCl(CO)(PPh3)(2)-catalyzed monomeric and dimeric cycloisomerization of propargylic 2,3-dienoates. Establishment of alpha,beta-unsaturated delta-lactone rings by cyclometallation
通讯作者	麻生明
英文摘要	Cyclometallation of two unsaturated carbon-carbon bonds usually requires the application of low-valent metal catalysts, which could cleave the propargylic ester linkage. Thus, it is desirable to identify a catalyst which could undergo cyclometallation without cleaving the propargylic ester linkage. In this paper, we used trans-RhCI(CO)(PPh3)(2) to realize the cyclometallation of propargylic 2,3-dienoates. The substituents at the 4-position of allenoate moiety nicely control the reaction pathway: when the 4-position of propargylic 2,3-dienoate 1 was monosubstituted with an aryl group, the bicyclic intermediate 7 formed by the cyclometallation could highly selectively undergo carbometalation with the alkyne moiety in the second molecule of propargylic 2,3-dienoate 1 to afford metallabicyclic intermediates 8a or 8b. Subsequent reductive elimination would afford 9, which could undergo an intramolecular Diels-Alder reaction resulting in the formation of polycyclic bis(delta-lactone)-containing structures 2. The intermediate could be trapped by adding 3-methoxyprop-1-yne affording cyclization-aromatization product 4p highly selectively. If the substituent at the 4-positon of the 2,3-allenoate moiety has a beta-H atom, sequential unimolecular cyclometallation/beta-H elimination/reductive elimination occurs to afford cross-conjugated 5(Z)-alkylidene-4-alkenyl-5,6-dihydropyran-2-ones. The Z-stereochemistry of the exo double bond was determined by the cyclometallation. Some of the a,p-unsaturated delta-lactones could be easily converted to other synthetically useful compounds via reduction reaction, hydrogenation, and iodination/coupling protocol.
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/ja073582u
语种	英语
WOS记录号	WOS:000249464900058
公开日期	2013-01-16
内容类型	期刊论文
源URL	[http://202.127.28.38/handle/331003/12094]
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	Jiang XF,Ma SM. trans-RhCl(CO)(PPh3)(2)-catalyzed monomeric and dimeric cycloisomerization of propargylic 2,3-dienoates. Establishment of alpha,beta-unsaturated delta-lactone rings by cyclometallation[J]. J. Am. Chem. Soc.,2007,129(37):11600-11607.
APA	姜雪峰,&麻生明.(2007).trans-RhCl(CO)(PPh3)(2)-catalyzed monomeric and dimeric cycloisomerization of propargylic 2,3-dienoates. Establishment of alpha,beta-unsaturated delta-lactone rings by cyclometallation.J. Am. Chem. Soc.,129(37),11600-11607.
MLA	姜雪峰,et al."trans-RhCl(CO)(PPh3)(2)-catalyzed monomeric and dimeric cycloisomerization of propargylic 2,3-dienoates. Establishment of alpha,beta-unsaturated delta-lactone rings by cyclometallation".J. Am. Chem. Soc. 129.37(2007):11600-11607.