Abstract
The hydrogenation of 5‐oxo‐5__H__‐5λ^5^‐dibenzophosphol‐5‐ol gives, almost quantitatively, only one geometric isomer of 5‐oxododecahydro‐5λ^5^‐dibenzophosphol‐5‐ol (2). An X‐ray structure analysis confirmed the formation of a meso isomer with a 4aβ,5aβ,9aβ,9bβ configuration (2a). Another possible way to get 2a is the hydrogenation of (4aβ,5aβ)‐5‐oxo‐2,3,4,4a,5,5a,6,7,8,9‐decahydro‐1__H__‐5λ^5^‐dibenzophosphol‐5‐ol (11), which is easily available starting from cyclohexanone. Highly selective epimerization has been achieved using LDA as base at elevated temperature. Resolution of 2e was achieved by salt formation with (R)‐(+)‐ and (S)‐(–)‐N‐benzyl‐α‐methylbenzylamine to give (+)‐ and (–)‐(4aα,5aβ,9aβ,9bβ)‐5‐oxododecahydro‐5λ^5^‐dibenzophosphol‐5‐ol. The geometry of 2e was confirmed by X‐ray structure analysis. Reduction of (+)‐ or (–)‐2e gave diastereomeric phospholanes (4aα,5__R__/S,5aβ,9aβ,9bβ)‐dodecahydrodibenzophosphole (1a), which were oxidized to the corresponding secondary phosphane oxides (SPOs) (4aα,5__R__/S,5aβ,9aβ,9bβ)‐dodecahydrodibenzophosphole 5‐oxide (1b). These phosphanes and phosphane oxides were used as ligands and preligands, respectively, in the Rh‐catalyzed enantioselective hydrogenation of benchmark substrates, where up to 79 % ee have been achieved. B3LYP density functional calculations reveal that among the three possible epimers at the ^4a^C‐ and ^5a^C‐positions the__chiral__ isomer (4aα,5aβ,9aβ,9bβ)‐5‐oxododecahydro‐5λ^5^‐dibenzophosphol‐5‐ol (2e) is 3.52 kcal mol^–1^ more stable than the related meso isomer 2a in Gibbs free energy. (© Wiley‐VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2006)