Stereoselective Pinacol-Type Rearrangement of 2,3-Epoxy Alcohols with Retention of Configuration Mediated by Bis(iodozincio)methane

The mechanisms of catalytic hydroxylation of unactivated C-H bonds by MMOH what is this? enzymes are not fully understood, however, and remain a subject of considerable research effort. Change-remove

The accumulated accumulated where? results of probe studies of MMO hydroxylations permit the firm conclusion that no radical intermediates are formed.

The rearrangement product from sMMO-catalyzed what is this? hydroxylation of methylcubane (1) is 1-homocubanol (4), formed via a cationic rearrangement, and production of a cationic species was also demonstrated in sMMO hydroxylation of probe 5. Rasshirit’

Stereoselective Pinacol-Type Rearrangement of 2,3-Epoxy Alcohols with Retention of Configuration Mediated by Bis(iodozincio)methane

The pinacol rearrangement has long been known to be difficult to control in terms of regioselectivity and stereoselectivity. Retention of the configuration is observed in the pinacol-type rearrangement of 2,3-epoxy alcohols 1 in the presence of bis(iodozincio)methane (2). The 1,3-migration of the hydroxymethyl group affords an intermediate 2-hydroxyaldehyde, which is methylenated by 2 in situ to give homoallyl alcohol 3. What about the inversion with methylaluminum bis(4-bromo-

2,6-di-tert-butylphenoxide? Investigated the universality of the reaction and determined the impact of substituents on the quality of its passage. Also one possible mechanism of the reaction was proposed.

Bold numbers, remove temperature, specify R

Date: 2014-12-22; view: 1210