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. 2008 Jul 23;130(29):9257-9.
doi: 10.1021/ja8031423. Epub 2008 Jun 27.

Efficient cross-coupling of secondary alkyltrifluoroborates with aryl chlorides--reaction discovery using parallel microscale experimentation

Spencer D Dreher  1 , Peter G Dormer, Deidre L Sandrock, Gary A Molander
Affiliations

Efficient cross-coupling of secondary alkyltrifluoroborates with aryl chlorides--reaction discovery using parallel microscale experimentation

Spencer D Dreher et al. J Am Chem Soc. .

Abstract

Microscale parallel experimentation was used to discover three catalyst systems capable of coupling secondary organotrifluoroborates with sterically and electronically demanding aryl chlorides and bromides. The ensuing results represent the first comprehensive study of alkylboron coupling to aryl chlorides and, in particular, using secondary alkylboron partners. A ligand-dependent beta-hydride elimination/reinsertion mechanism was implicated in the cross-coupling of more hindered substrates, leading to isomeric mixtures of coupled products in some cases.

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Figures

Figure 1
Figure 1
Relative reactivity and selectivity (i-Pi vs n-Pr) of various electrophiles using n-BuPAd2, t-Bu3P and t-Bu2PPh. All reactions used Cs2CO3 (3 equiv), 10:1 toluene/H2O, Pd(OAc)2 (2 mol %), ligand (3 mol %), i-PrBF3K (1.1 equiv), 18 h, 100 °C.
Scheme 1
Scheme 1
See this image and copyright information in PMC

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