The stereoselective synthesis of tetrasubstituted olefins remains an active area of research in the synthetic community. The synthesis of a drug candidate at Genentech involved producing such an olefin functional group. During those synthetic efforts we discovered and developed a general and scaleable method that allows for the modular, stereocontrolled synthesis of tetrasubstituted olefins through the stereoselective formation of enol tosylates from the corresponding ketones using LiHMDS and a trialkylamine base, followed by Suzuki cross coupling reactions with arylboronates. A combination of NMR spectroscopy and DFT calculations were enlisted to probe the origins of the high stereoselectivity in the key enolization step, thus providing key insights into the mechanism of this transformation.

Stereoselective formation of tetrasubstituted olefins via enol tosylate formation

253rd National Meeting (2017)

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