New P-stereogenic triaminophosphines and their derivatives: synthesis, structure, conformational study, and application as chiral ligands

The synthesis, structural, and conformational studies of new P-chiral triaminophosphines, which feature an indolidine and a 1,2,3,4-tetrahydroquinolidine pattern, respectively, are reported. These compounds can feature very different 3D-structures, although they both could be seen a priori as close derivatives of the previously reported 3-phenyl-1,3-diaza-2-phosphabicyclo[3.3.0]octane. The consequences for the use of such compounds and their derivatives in asymmetric metal-catalysis are discussed on the basis of preliminary results in asymmetric cobalt-catalyzed [6+2] cycloaddition.

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(2SP,5SC)-2-Dimethylamino-3-phenyl-1,3-diaza-2-phosphabenzo[7,8]bicyclo[3.3.0]octaneC17H20N3P[α]D20=-60 (c 0.74, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: (2SP,5SC)

(6SC,7RP)-9-Dimethylamino-8-phenyl-1,8-diaza-9-phosphabenzo[3,4]bicyclo[4.3.0]nonaneC18H22N3P[α]D20=-176 (c 0.80, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: (6SC,7RP)

(2SP,5SC)-2-Phenoxy-3-phenyl-1,3-diaza-2-phosphabenzo[7,8]bicyclo[3.3.0]octaneC21H19N2OP[α]D20=-176 (c 1.0, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: (2SP,5SC)

(2SP,5SC)-2-(Ortho-phenylphenoxy)-3-phenyl-1,3-diaza-2-phosphabenzo[7,8]bicyclo[3.3.0]octaneC27H23N2OP[α]D20=-187 (c 0.76, CH2Cl2)Source of chirality: asymmetric synthesisAbsolute configuration: (2SP,5SC)