Nucleophilic addition of o-tolyllithium compounds to di-tert-butyl ketone. Thermal and organolithium-catalyzed isomerization of o-tolyldi-tert-butylcarbinol rotamers

JS Lomas, PK Luong, JE Dubois

Index: Lomas,J.S. et al. Journal of Organic Chemistry, 1977 , vol. 42, # 21 p. 3394 - 3399

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Citation Number: 32

Abstract

Addition of ring-substituted o-tolyllithium compounds to di-tert-butyl ketone gives rise to rotamers, syn-(sp) and anti-periplanar (ap) o-tolyldi-tert-butylcarbinols, the latter representing about 85-93% of the total, depending on the substituent. The ap isomer can be thermally isomerized to the sp form which, according to empirical force field calculations, is 6 kcal/mol more stable than the other. The IR and NMR spectra reveal marked similarities ...