High regio-, chemo-, and stereoselectivity via low-temperature 4 + 3 cycloadditions. Convergent synthesis of multifunctionalized vinylmetals (M = Si, Sn) and S-vinyl benzenecarbothioates
A series of enantiomerically pure 8-oxabicyclo[3.2.1]oct-6-en-3-ones functionalized in the unsaturated two-carbon bridge has been prepared by the title reaction. Carbocation reactivity has been fined-tuned at -95 degrees C and adjusted to diene nucleophilicity. Conventional electrophilic substitution of 3-silylated and 3-stannylated furan is suppressed in favor of the rapid 4 + 3 cycloaddition mode. In the case of cycloadduct 13A, stereoselectivity (17:1) is perfectly matched to regioselectivity (17:1). High stereoselection as well as unprecedented regioselection and chemoselection is attributed to the low-temperature cycloaddition protocol and the design of chiral auxiliary and tether.
Beck
H
Department of Organic Chemistry, University of Hannover, Germany.
Stark
CB
Hoffmann
HM