Chlorohydrins, olefin oxidation synthesis

Chloroform stability, lipid hydroperoxides, 676 Chlorohydridosilane, alkyl sodium alkyl peroxide reaction, 783 Chlorohydrins, olefin oxidation synthesis, 792-3... 

Chiral alkenyl and cycloalkenyl oxiranes are valuable intermediates in organic synthesis [38]. Their asymmetric synthesis has been accomplished by several methods, including the epoxidation of allyl alcohols in combination with an oxidation and olefination [39a], the epoxidation of dienes [39b,c], the chloroallylation of aldehydes in combination with a 1,2-elimination [39f-h], and the reaction of S-ylides with aldehydes [39i]. Although these methods are efficient for the synthesis of alkenyl oxiranes, they are not well suited for cycloalkenyl oxiranes of the 56 type (Scheme 1.3.21). Therefore we had developed an interest in the asymmetric synthesis of the cycloalkenyl oxiranes 56 from the sulfonimidoyl-substituted homoallyl alcohols 7. It was speculated that the allylic sulfoximine group of 7 could be stereoselectively replaced by a Cl atom with formation of corresponding chlorohydrins 55 which upon base treatment should give the cycloalkenyl oxiranes 56. The feasibility of a Cl substitution of the sulfoximine group had been shown previously in the case of S-alkyl sulfoximines [40]. 

El-Qisairi, A. K., Qaseer, H. A., Henry, P. M. Oxidation of olefins by palladium(ll). 18. Effect of reaction conditions, substrate structure and chiral ligand on the bimetallic palladium(ll) catalyzed asymmetric chlorohydrin synthesis. J. Organomet. Chem. 2002, 656,168-176. 

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