The ability to selectively transform inexpensive feedstock materials into value-added products remains a goal in the field of chemistry. Although unactivated olefins are ideal substrates for chemical synthesis, they also present a challenge when attempting to selectively differentiate between sterically and electronically similar C-H bonds. We have developed a general strategy for the synthesis of value-added internal olefin products from readily available terminal olefins and Grignard reagents. This process proceeds through a hetero-ene reaction of terminal olefins with a commercially available sulfurdiimide oxidant followed by a copper-catalyzed SN2 allylic alkylation with aliphatic, aromatic and vinyl Grignard reagents. Products are generated in high yields with broad substrate scope and selective formation of E-olefins. This one-pot transformation has been utilized for the synthesis of a variety of skipped dienes from polyunsaturated materials through the regulation of mono- and bis-functionalization.

Allylic functionalization of unactivated olefins with Grignard reagents

247th National Meeting (2014)

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