Iridium-Catalyzed Stereoselective Allylic Alkylation Reactions with Crotyl Chloride
The development of the first enantio-, diastereo-, and regioselective iridium-catalyzed allylic alkylation reaction of prochiral enolates to form an all-carbon quaternary stereogenic center with an aliphatic-substituted allylic electrophile is disclosed. The reaction proceeds with good to excellent selectivity with a range of substituted tetralone-derived nucleophiles furnishing products bearing a newly formed vicinal tertiary and all-carbon quaternary stereodyad. The utility of this protocol is further demonstrated via a number of synthetically diverse product transformations.
Additional Information© 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim. Manuscript received: October 11, 2016; Revised: October 27, 2016; First published: 28 November 2016. The NIH-NIGMS (R01GM080269) and Caltech are thanked for support of our research program. Additionally, J.C.H. thanks the Camille and Henry Dreyfus postdoctoral program in Environmental Chemistry, and S.E.S. thanks the NIG-NIGMS for a predoctoral fellowship (F31GM120804). Dr. David VanderVelde is thanked for assistance with structural assignments via NMR analysis. Dr. Michael Takase, Dr. Lawrence Henling, and Niklas Thompson are acknowledged for X-ray analyses. Dr. Mona Shahgholi and Naseem Torian are thanked for mass spectrometry assistance. Dr. Scott Virgil is thanked for instrumentation assistance. Prof. Wen-bo Liu is thanked for helpful discussions.
Accepted Version - nihms835913.pdf
Supplemental Material - anie201609960-sup-0001-misc_information.pdf