A full account of the novel and flexible approach to hydroxylated 8-azabicyclo[3,2,1]octan-3-ones and 9-azabicyclo[3,3,1] nonan-3-ones is presented. Using keto-lactams as the starting materials, this two-step method c...A full account of the novel and flexible approach to hydroxylated 8-azabicyclo[3,2,1]octan-3-ones and 9-azabicyclo[3,3,1] nonan-3-ones is presented. Using keto-lactams as the starting materials, this two-step method consists of silyl enol ether for mation with TBDMSOTf, lactam activation with Tf20/DTBMP, and halide-promoted cyclization. Radical dechlorination of the resulting 1-halotropan-3-ones led to the corresponding hydroxylated tropan-3-ones, which can be hydrogenated to yield 3ct,613-dihydroxytropanes. Starting from optically active keto-lactams, the method has been applied to the enantioselective syntheses of （＋）-（1S,3S,5R,6S）-pervilleine C （6）, （＋）-（1S,3R,5S,6R）-valeroidine （3）, （＋）-（1S,3S,5R,6S）-dibenzoyloxytropane （8） and （＋）-（1S,3S,5R,6S）-merredissine （9）.展开更多
基金the National Basic Research Program of China(973 Program,2010CB833200)the National Natural Science Foundation of China(21072160,21332007)the Program for Changjiang Scholars and Innovative Research Team at the University of the MOE for financial support
文摘A full account of the novel and flexible approach to hydroxylated 8-azabicyclo[3,2,1]octan-3-ones and 9-azabicyclo[3,3,1] nonan-3-ones is presented. Using keto-lactams as the starting materials, this two-step method consists of silyl enol ether for mation with TBDMSOTf, lactam activation with Tf20/DTBMP, and halide-promoted cyclization. Radical dechlorination of the resulting 1-halotropan-3-ones led to the corresponding hydroxylated tropan-3-ones, which can be hydrogenated to yield 3ct,613-dihydroxytropanes. Starting from optically active keto-lactams, the method has been applied to the enantioselective syntheses of （＋）-（1S,3S,5R,6S）-pervilleine C （6）, （＋）-（1S,3R,5S,6R）-valeroidine （3）, （＋）-（1S,3S,5R,6S）-dibenzoyloxytropane （8） and （＋）-（1S,3S,5R,6S）-merredissine （9）.
