Synthesis of a New Chiral Cyclic o-Hydroxynaphthylphosphonodiamide and its Application as Ligand Catalyst in Asymmetric Silylcyanation of Aromatic Aldehydes

Abstract

A new chiral cyclic o-hydroxynaphthylphosphonodi­amide (+)-2 was synthesized starting from (+)-cis-1,2,2-trimethylcyclopentane-1,3-diamine. The absolute configuration of phos-phorus atom was determined as S by X-ray diffraction analysis. ­Excellent enantioselectivity (up to 98.3% ee) was achieved in asymmetric silylcyanation of aromatic aldehydes using a chiral titanium complex prepared in situ from Ti(Oi-Pr)₄ and (+)-2 as the catalyst.

chiral phosphonodiamide - asymmetric silylcyanation - catalysis - enantioselectivity - aromatic aldehyde

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General procedure for the asymmetric silylcyanation of aromatic aldehydes:

To a solution of (+)-(S)-2 (0.275 g, 0.54 mmol) in 5 mL of methylene chloride was added Ti(OPr-i)₄ (37.2 mL, 0.13 mmol) under a nitrogen atmosphere at 20 °C and resulting mixture was stirred for 1 h at the same temperature. Then iso-propanol (15.6 mL, 0.26 mmol), 2 mL of methylene chloride, benzaldehyde (0.142 g, 1.34 mmol) and trimethylsilyl cyanide (200 mL, 16 mmol) were added to it and the whole stirred for 24 h at the same temperature. After determination of the enantiomeric excess value of the cyanohydrin trimethylsilylether by chiral HPLC, the mixture was poured into a mixture of 1 N HCl (30 mL) and ethyl acetate (40 mL) and stirred vigorously for 6 h. The organic layer was separated and the aqueous layer was extracted with ethyl acetate (2 ¥ 20 mL). The combined organic phase was washed with brine and dried over anhydrous magnesium sulfate. After removal of solvent the residue was purified by thin layer chromatography on silica gel to afford 150 mg (84% yield) of the corresponding cyanohydrin. [a]_D ²⁰ +23.8 (c 1, CHCl3), 1H NMR (d, CHCl₃): 3.51 (s, 1H, OH), 5.48 (d, 1H, CH), 7.43-7.49 (m, 5H, 5 H_arom).

Spectroscopic data for all prepared compounds are available from the authors.