Molecular rearrangements Brook rearrangement

A. G. Brook and A. R. Bassindale. Molecular rearrangements of organosilicon compounds. Rearrangements in Ground and Excited States, ed. P. de Mayo. Vol. 2. Academic Press. New York (1980). 

Brook, A.G. (1974). Some molecular rearrangements of organosilicon compounds. Accounts of Chemical. Research, 7, 77-84. 

Oxasilacyclopentenes were shown to be competent substrates for a scandium triflate-catalyzed Mukaiyama aldol process (Scheme 7.35).104 Exposure of silacy-clopentene 121 and benzaldehyde to substoichiometric amounts of scandium triflate produced ketone 122 diastereoselectively.105 This ketone was proposed to form by addition of enolate 123, resulting from desilylation of 121,106 to benzaldehyde. A 1,3-Brook rearrangement then afforded 122 from 124.107 This ketone could be further functionalized through lithium aluminum hydride reduction followed by deprotection to afford triol 125 containing four contiguous stereocenters. Thus, the molecular complexity of silyloxyalkynes can be increased dramatically in just three operations. 

Woodcock HL, M Hodoscek, P Sherwood, YS Lee, HF Schaefer, BR Brooks (2003) Exploring the quantum mechanical/molecular mechanical replica path method a pathway optimization of the chorismate to prephenate Claisen rearrangement catalyzed by chorismate mutase. Theor. Chem. Acc. 109 (3) 140-148... 

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