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Stereospecific, Nickel-Catalyzed Suzuki–Miyaura Cross-Coupling of Allylic Pivalates To Deliver Quaternary Stereocenters

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journal contribution
posted on 07.08.2017, 16:15 by Kelsey M. Cobb, Javon M. Rabb-Lynch, Megan E. Hoerrner, Alex Manders, Qi Zhou, Mary P. Watson
Recognizing the importance of all-carbon, quaternary stereocenters in complex molecule synthesis, a stereospecific, nickel-catalyzed cross-coupling of allylic pivalates with arylboroxines to deliver products equipped with quaternary stereocenters and internal alkenes was developed. The enantioenriched allylic pivalate starting materials are readily prepared, and a variety of functional groups can be incorporated on both the allylic pivalate and the arylboroxine. Additional advantages include the use of a commercially available and air-stable Ni­(II) salt and BISBI ligand, mild reaction conditions, and high yields and ee’s. The observed stereoinversion of this reaction is consistent with an open transition state in the oxidative addition step.