The fragmentation of 7-norbornyloxychlorocarbene SNi-like transition states
Keyword(s):
7-Norbornyloxychlorocarbene (15) fragments mainly to 7-norbornyl chloride (16). A C-2 deuterated analog of 15 (syn-15-d) fragments to labeled chloride 16 with 78% retention and 22% inversion. When the deuterium label is replaced by a syn-exo-2-methyl group, the resultant carbene 22 fragments to syn- and anti-7-chloro-exo-2-methylnorbornane in a ratio of 1:1.1, corresponding to 48% retention and 52% inversion. Computational studies suggest that the fragmentations proceed via competitive SNi-like transition states that lead to either retention or inversion. Key words: carbenes, carbocations, SNi reactions, stereochemistry.
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2002 ◽
Vol 67
(10)
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pp. 1517-1532
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1995 ◽
Vol 102
(1)
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pp. 161-169
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2004 ◽
Vol 2
(17)
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pp. 2426-2436
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