biostudies-literatureYang DNIGMS NIH HHS2144-2147https://www.ebi.ac.uk/biostudies/studies/S-EPMC3110011biostudies-literatureUnknown52(17)Regioselective titanium alkoxide-mediated reductive cross-coupling reactions of allylic alcohols with vinylsilanes and imines have previously been demonstrated to proceed with allylic transposition by formal metallo-[3,3]-rearrangement [thought to proceed by a sequence of: 1) directed carbometalation, and 2) syn-elimination]. While many examples have been described that support this reaction path, a collection of substrates have recently been identified that react by way of an alternative pathway, delivering a concise convergent route to coupled products bearing a quaternary center.Tetrahedron lettersGeneration of quaternary centers by reductive cross-coupling: shifting of regioselectivity in a subset of allylic alcohol-based coupling reactions.PMC3110011R01 GM080266R01 GM080266-05Micalizio GCBelardi JKYang DfalseGeneration of quaternary centers by reductive cross-coupling: shifting of regioselectivity in a subset of allylic alcohol-based coupling reactions.Regioselective titanium alkoxide-mediated reductive cross-coupling reactions of allylic alcohols with vinylsilanes and imines have previously been demonstrated to proceed with allylic transposition by formal metallo-[3,3]-rearrangement [thought to proceed by a sequence of: 1) directed carbometalation, and 2) syn-elimination]. While many examples have been described that support this reaction path, a collection of substrates have recently been identified that react by way of an alternative pathway, delivering a concise convergent route to coupled products bearing a quaternary center.2011-01-01T00:00:00Z2011 Apr2024-10-18T00:58:47.597Z2019-03-27T00:42:21ZS-EPMC31100112166683210.1016/j.tetlet.2010.11.059