Catalytic system for heck reactions involving insertion into Pd-(perfluoro-organyl) bonds
Catalytic system for heck reactions involving insertion into Pd-(perfluoro-organyl) bonds
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DOI：
10.1021/ja016315b
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发表时间：
2001-11-21
影响因子：
15
通讯作者：
Milstein, D
中科院分区：
文献类型：
--
作者：
Albéniz, AC;Espinet, P;Milstein, D
ReVised Manuscript ReceiVed October 11, 2001 σ-Bonds between transition metals and perfluorinated groups (M-Rf) are among the strongest MC bonds. Very few stoichiometric and, as far as we know, no catalytic reactions based on insertion of unsaturated molecules into M-Rf bonds have been reported. Alkene insertion into MC bonds plays a key role in important catalytic processes such as alkene oligomerization, 1 polymerization, 1a, 2 and the Heck reaction. 3 Such catalysis involving M-Rf bonds is desirable for the functionalization of perfluorinated compounds, important for the fine chemical and pharmaceutical industries. 4In recent years the Heck reaction has been improved by the discovery of very active catalysts based on palladacycles, or the use of new reaction conditions, 5-8 but despite the major effort in this field, perfluoro-aryl or-alkyl halides have not been reported as substrates. 9 Here we report the first catalytic Heck reaction, involving olefin insertion into an Rf-M bond. Some of us had studied the insertion of dienes into the Pd-Pf bond of [Pd (Pf) Br (NCMe) 2](1) and (NBu4) 2 [Pd2 (μ-Br) 2 (Pf) 2Br2](2a)(Pf) C6F5) and isolated intermediates relevant in the Heck reaction. 10, 11 The stoichiometric reaction of 2a and styrene in the presence of a silver salt gave trans-PhCHdCHPf, 11 which encouraged us to look for catalytic conditions for it. Indeed 1
