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. 2012 Jul 18;134(28):11372-5.
doi: 10.1021/ja304344h. Epub 2012 Jul 10.

Palladium-catalyzed 1,1-difunctionalization of ethylene

Vaneet Saini  1 , Matthew S Sigman
Affiliations

Palladium-catalyzed 1,1-difunctionalization of ethylene

Vaneet Saini et al. J Am Chem Soc. .

Abstract

The 1,1-difunctionalization of ethylene, with aryl/vinyl/heteroaryl transmetalating agents and vinyl electrophiles, is reported. The reaction is high-yielding under a low pressure of ethylene, and regioselectivity is generally high for the 1,1-disubstituted product. The process is highlighted by the use of heteroaromatic cross-coupling reagents, which have not been competent reaction partners in previously reported efforts.

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Figures

Figure 1
Figure 1
Scope of the Three Component Coupling of Ethylene, Vinyl Nonaflates, and Vinyl Boronic acids/esters. Regioselectivity of 3:4 in parentheses a) Boronic acid was used. b) Boronic acid pinacol ester was used. Note: 1) In the case of 3u and 3v, cyclohexenyl nonaflate was used as an electrophile. 2) yields are reported as a mixture of regioisomers. 3) The products were accompanied by polyethylene as a contaminant.
Scheme 1
Scheme 1
Proposed 1,1 Difunctionalization of Ethylene with Vinyl Electrophiles and Boronic Acids.
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