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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
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
Jiang XF(姜雪峰); Ma SM(麻生明)
2007
发表期刊J. Am. Chem. Soc.
ISSN0002-7863
卷号129期号:37页码:11600-11607
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.
学科领域金属有机化学
部门归属上海有机所
URL查看原文
收录类别SCI
语种英语
WOS记录号WOS:000249464900058
引用统计
被引频次:39[WOS]   [WOS记录]     [WOS相关记录]
文献类型期刊论文
条目标识符http://ir.sioc.ac.cn/handle/331003/12094
专题金属有机化学国家重点实验室
通讯作者Ma SM(麻生明)
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.
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