ol7b02063_si_001.pdf (9.64 MB)
Stereospecific, Nickel-Catalyzed Suzuki–Miyaura Cross-Coupling of Allylic Pivalates To Deliver Quaternary Stereocenters
journal contribution
posted on 2017-08-07, 16:15 authored by Kelsey
M. Cobb, Javon M. Rabb-Lynch, Megan E. Hoerrner, Alex Manders, Qi Zhou, Mary P. WatsonRecognizing
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.