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学科主题: 金属有机化学
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
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
作者: Jiang XF(姜雪峰) ; Ma SM(麻生明)
通讯作者: 麻生明
刊名: J. Am. Chem. Soc.
发表日期: 2007
卷: 129, 期:37, 页:11600-11607
收录类别: SCI
部门归属: 上海有机所
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.
语种: 英语
相关网址: 查看原文
WOS记录号: WOS:000249464900058
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内容类型: 期刊论文
URI标识: http://ir.sioc.ac.cn/handle/331003/12094
Appears in Collections:金属有机化学国家重点实验室_期刊论文

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Recommended Citation:
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.
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