ja074300t_si_001.pdf (6.66 MB)
Download fileTotal Synthesis of (−)-Sarain A
journal contribution
posted on 2007-10-03, 00:00 authored by Michael H. Becker, Peter Chua, Robert Downham, Christopher J. Douglas, Neil K. Garg, Sheldon Hiebert, Stefan Jaroch, Richard T. Matsuoka, Joy A. Middleton, Fay W. Ng, Larry E. OvermanThis article describes the details of our synthetic studies toward the complex marine alkaloid
sarain A. Various strategies were conceived, setbacks encountered, and solutions developed, ultimately
leading to a successful enantioselective total synthesis. Our route to (−)-sarain A features a number of
key steps, including an asymmetric Michael addition to install the C4‘−C3‘−C7‘ stereotriad, an enoxysilane-N-sulfonyliminium ion cyclization to set the C3 quaternary carbon stereocenter, and assemble the
diazatricycloundecane core, a ring-closing metathesis to construct the 13-membered ring, an intramolecular
Stille coupling to fashion the unsaturated 14-membered macrocycle, and a late-stage installation of the
tertiary amine−aldehyde proximity interaction.
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diazatricycloundecane corefashioncyclizationproximitysetbackVarious strategiesaminemacrocycleenantioselectiveMichael additionC 3 quaternary carbon stereocenterAThistrategyintramolecular Stilleinstallationsynthesismetathesimemberedarticlemarine alkaloid saraininteractionSarainTotal Synthesissolutionstereotriad