Synthesis and separation into enantiomers of ?-(N,N'-dimethylaminomethyl)formylcymantrene

Ionic and Organometallic‐Catalyzed Organosilane Reductions

“…A study of the reduction of 2-methyl-1phenylpropan-1-ol (21, R = OH) and its isomer, 2-methyl-1-phenylpropan-2-ol (22, R = OH), illustrates this observation. 166 Both of these alcohols are reduced in high yield (98%) by the action of acid and triphenylsilane to the same hydrocarbon, 2-methyl-1-phenylpropane (21 or 22, R = H). The immediate products formed from either alcohol in a 55% solution of trifluoroacetic acid in nitrobenzene are the trifluoroacetate esters (R = CF 3 CO 2 ).…”

“…The conclusion is reached that the species actually captured by the organosilicon hydride consists of a dynamic mixture of the two cations derived from 21 and 22. 166 Ph R Ph R 21 22 In some instances, treatment of polyfunctional benzylic alcohols with acid in the presence of organosilicon hydrides causes multiple functional group transformations to occur simultaneously. This phenomenon is illustrated by the reduction of the secondary benzylic alcohol function and concomitant loss of the methoxymethyl protecting group of 2-(1-hydroxydecyl)-5-methoxy-1-(methoxymethyleneoxy)naphthalene upon treatment with Et 3 An example of an exclusive chemoselective reduction of a benzylic hydroxy function in a polyfunctional compound is seen in the conversion of 23 into 24 in 76% yield using Et 3 SiH/TFA (Eq.…”