Experimental and computational evidence for gold vinylidenes: generation from terminal alkynes via a bifurcation pathway and facile C-H insertions.
Experimental and computational evidence for gold vinylidenes: generation from terminal alkynes via a bifurcation pathway and facile C-H insertions.
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DOI：
10.1021/ja2091992
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发表时间：
2012-01-11
影响因子：
15
通讯作者：
Zhang, Liming
中科院分区：
文献类型：
--
作者：
Ye, Longwu;Wang, Yanzhao;Aue, Donald H.;Zhang, Liming
两个BrettPhosAuNTf2分子协同促进了(2-乙炔基苯基)炔烃的简易环异构化反应，得到了产率较高的三环吲哚。根据机理研究和理论计算，最有可能生成的是金偏二烯作为反应中间体之一。与已知的Rh、Ru和W不同，这种新的金物种具有高活性，可以方便地在分子内进行C(SP3)-H插入以及O-H和N-H插入。从理论上预测了金偏二烯的形成步骤是一个具有分叉反应路径的复杂步骤。吡啶N-氧化物作为弱碱促进了炔基金中间体的形成，而金催化剂中笨重的BrettPhos配体可能在空间上引导反应向金偏二烯的形成方面起到了作用。
Facile cycloisomerization of (2-ethynylphenyl)alkynes is proposed to be promoted synergistically by two molecules of BrettPhosAuNTf2, affording tricyclic indenes in mostly good yields. A gold vinylidene is most likely generated as one of the reaction intermediates based on both mechanistic studies and theoretical calculations. Different from the well-known Rh, Ru and W counterparts, this novel gold species is highly reactive and undergoes facile intramolecular C(sp3)-H insertions as well as O-H and N-H insertions. The formation step for the gold vinylidene is predicted theoretically to be complex with a bifurcated reaction pathway. The pyridine N-oxide acts as a weak base to facilitate the formation of an alkynylgold intermediate, and the bulky BrettPhos ligand in the gold catalyst likely plays a role in sterically steering the reaction toward the gold vinylidene formation.
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影响因子：
15
作者：
Bhunia, Sabyasachi;Liu, Rai-Shung
通讯作者：
Liu, Rai-Shung
影响因子：
15
作者：
He, Weimin;Li, Chaoqun;Zhang, Liming
通讯作者：
Zhang, Liming
影响因子：
15
作者：
Horino Y;Yamamoto T;Ueda K;Kuroda S;Toste FD
通讯作者：
Toste FD
影响因子：
5.2
作者：
Benitez D;Tkatchouk E;Gonzalez AZ;Goddard WA 3rd;Toste FD
通讯作者：
Toste FD
DOI：
10.1016/0090-6980(94)90060-4
发表时间：
1994-03-01
期刊：
PROSTAGLANDINS
影响因子：
--
作者：
JAKUBOWSKI, JA;UTTERBACK, BG;FUCHS, PL
通讯作者：
FUCHS, PL