J Org Chem. 1999 Nov 26;64(24):8862-8867. doi: 10.1021/jo991091p.

Functional-Group-Directed Diastereoselective Hydrogenation of Aromatic Compounds. 1.

The Journal of organic chemistry

Vidyadhar S. Ranade, Giambattista Consiglio, Roel Prins

PMID: 11674790 DOI: 10.1021/jo991091p

Abstract

Diastereoselective liquid phase hydrogenation of a series of monosubstituted indane and tetralin substrates was studied on supported rhodium catalysts. Predominantly the cis-cis diastereomer, obtained by hydrogenation from the diastereoface opposite the substituent (at the stereogenic center), and the cis-trans diastereomer, obtained by hydrogenation from the diastereoface on the same side as the substituent, were formed. The diastereoselectivity between the two isomers was dependent on the steric repulsion or the electronic attraction of the substituent with the surface of the catalyst. The hydroxyl group did not exhibit a strong attraction (haptophilicity), and the cis-cis diastereomer was obtained as the major product. The amino group exhibited a very high haptophilicity, yielding primarily the cis-trans diastereomer. The diastereoselectivity obtained in the hydrogenation of all the substrates was influenced on addition of bases to the reaction mixture. In the case of alcoholic substrates, the selectivity to the cis-trans diastereomer could be substantially increased with alkaline hydroxide additives.

Publication Types

• Journal Article