Palladium-catalyzed [2+2+2] cocyclotrimerization of benzynes with bicyclic alkenes: An efficient route to anellated 9,10-dihydrophenanthrene derivatives and polyaromatic compounds

被引:73
作者
Jayanth, TT [1 ]
Jeganmohan, M [1 ]
Cheng, CH [1 ]
机构
[1] Natl Tsing Hua Univ, Dept Chem, Hsinchu 30013, Taiwan
关键词
D O I
10.1021/jo048702k
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
An efficient method for the cocyclotrimerization of bicyclic alkenes and benzynes catalyzed by palladium phosphine complexes to give the corresponding norbornane anellated 9,10-dihydrophenanthrene derivatives is described. Bicyclic alkenes 1a-i undergo [2 + 2 + 2] cocyclotrimerization with benzynes generated from precursors 2a-d [2-(trimethylsilyl)phenyl triflate (2a), 4,5-dimethyl-2-(trimethylsilyl)phenyl triflate (2b), 6-(trimethylsilyl)-2,3-dihydro-1H-5-indenyl triflate (2c), 4-methyl-2-(trimethylsilyl)phenyl triflate (2d)] in the presence of PdCl2(PPh3)(2) in acetonitrile at ambient temperature to yield anellated 9,10-dihydrophenanthrene products 3a-r in moderate to excellent yields. The [2 + 2 + 2] cocyclotrimerization products from oxa- and azabicyclic alkenes can be applied for the synthesis of polyaromatics, substituted benzo[b]triphenylenes (8a-f), via a simple Lewis acid mediated deoxyaromatization in good yields. In addition the [2 + 2 + 2] products undergo retro Diels-Alder reaction readily, providing a new method for the synthesis of substituted phenanthrenes and for generating isobenzofurans. A plausible mechanism is proposed to account for the catalytic [2 + 2 + 2] cycloaddition reaction.
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页码:8445 / 8450
页数:6
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