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. 2014 Jul 16;136(28):10166-72.
doi: 10.1021/ja505446y. Epub 2014 Jul 8.

Rational design of a second generation catalyst for preparation of allylsilanes using the silyl-Heck reaction

Jesse R McAtee  1 , Glenn P A Yap, Donald A Watson
Affiliations

Rational design of a second generation catalyst for preparation of allylsilanes using the silyl-Heck reaction

Jesse R McAtee et al. J Am Chem Soc. .

Abstract

Using rational ligand design, we have developed of a second-generation ligand, bis(3,5-di-tert-butylphenyl)(tert-butyl)phosphine, for the preparation of allylsilanes using the palladium-catalyzed silyl-Heck reaction. This new ligand provides nearly complete suppression of starting material alkene isomerization that was observed with our first-generation catalyst, providing vastly improved yields of allylsilanes from simple alkene starting materials. The studies quantifying the electronic and steric properties of the new ligand are described. Finally, we report an X-ray crystal structure of a palladium complex resulting from the oxidative addition of Me3SiI using an analogous ligand that provides significant insight into the nature of the catalytic system.

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Figures

Figure 1
Figure 1
Rational design of 2nd generation catalyst for the silyl-Heck reaction.
Figure 2
Figure 2
Conformational analysis of dimethylamino group in ligand 11.
Figure 3
Figure 3
Scope of silyl-Heck reaction to form allylsilanes with second-generation ligand.
Figure 4
Figure 4
Silyl-Heck reactions with aryl-substituted allyl substrates.
Scheme 1
Scheme 1. Kinetic Stability of Vinylsilanes Under Silyl-Heck Reaction Conditions
Figure 5
Figure 5
Steric vs Electronic Control in β-Hydride Elimination Leading to Product 29.
Figure 6
Figure 6
Preparation and structure of complex 39.
See this image and copyright information in PMC

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