Journal of the American Chemical Society
Communication
nucleophiles. While we recognize this possibility, we consider it
unlikely because the KIE studies2c indicated that the β-O-mannosides
are formed by a highly associative pathway that is different from the
one for the formation of the α-O-mannosides, at least in the 4,6-O-
benzylidene series.
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(19) The cis-fused compound 5 is not necessarily formed exclusively
from the B2,5 boat conformer of oxocarbenium ion 8. Other
conformers unable to achieve trans cyclization leading to 6 (e.g., the
4H3 half-chair) are well-suited to undergo concomitant cis cyclization
to give 5.
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(21) The possibility that a minor portion of β-O-mannoside 9 is
formed by the dissociative mechanism cannot be excluded.
(22) This difference in transition states and selectivity does not
preclude the use of a clock reaction to determine the relative rates, as
demonstrated by the classical use of the 5-hexenyl radical cyclization
reaction to estimate the rate of H atom abstraction from
tributylstannane.8
(23) It could also be considered that β-O-mannoside 9 arises from
reaction with oxocarbenium ion 8, in which case the latter would
exhibit a strong inherent β-selectivity toward both C and O
D
dx.doi.org/10.1021/ja307266n | J. Am. Chem. Soc. XXXX, XXX, XXX−XXX