Studies on the stereochemistry of reduction reactions on 10-R substituted trans decal-2-Ones

Inductive and Resonance Effects of Substituents on π-Face Selection

“…The effect of γ-substitution was examined in the series of 4-X-cyclohexanones and 10-X- trans -decal-2-ones. ,,, The results obtained with the latter ketones confirm that the effect of substitution on the reaction rate depends on the nature of the nucleophile, see Figure and Scheme . The axial γ-ethoxycarbonyl group in 10-carbethoxy- trans -decal-2-one slows down the equatorial alkylation reactions within the series (CH 3 ) 3 Al 1:1/C 6 H 6 , CH 3 Li/(CH 3 ) 2 CuLi, CH 3 Li, CH 3 MgI (no effect on (CH 3 ) 3 Al 3:1) but accelerates the axial alkylations except for (CH 3 ) 3 Al 1:1/C 6 H 6 …”

“…Similarly, the effect of the C(10)-methoxycarbonyl group on the rate of reduction of trans -decal-2-one depends on the hydride . Both equatorial and axial NaBH 4 reductions are accelerated, but in the case of LiAlH 4 and LiBEt 3 H, acceleration of the axial reductions is minimal, see Figure , while the equatorial reductions are slowed down.…”

“…The effect of γ-substitution on the stereochemistry of nucleophilic additions to cyclohexanones was investigated in metal hydride reductions, organometallic alkylations, and sulfur ylide alkylations of 4-X-cyclohexanones, ,, 2-, 3-, and 4- tert -butyl-4-X-cyclohexanones, − 10-X- trans -decal-2-ones, ,,,, and 4-X- trans -decal-1-ones. , It is useful in this discussion to consider separately the effect of the equatorial and axial γ-substitution.…”

Decarboxylative Halogenation of Organic Compounds

“…Noticeably, the unsaturated moieties are tolerated ( 176 , 184 , 185 ), unless the double bond is favorably located toward intramolecular radical cyclization. Interestingly, suitably located unprotected hydroxy groups do not affect the course of the reaction ( 179 ) . The chlorodecarboxylation of alpha-substituted carboxylic acids was shown to proceed in good yields.…”

“…Interestingly, suitably located unprotected hydroxy groups do not affect the course of the reaction (179). 127 The chlorodecarboxylation of alpha-substituted carboxylic acids was shown to proceed in good yields. Thus, α-chloroamide 137 169 and 2-chlorooxetane 125 170 derivatives were successfully prepared.…”