Bifunctional Iminophosphorane Catalyzed Enantioselective Ketimine Phospha-Mannich Reaction

Gerard P. Robertson; Alistair J. M. Farley; Darren J. Dixon

doi:10.1055/s-0035-1560530

Synlett, Table of Contents

Synlett 2016; 27(01): 21-24
DOI: 10.1055/s-0035-1560530

letter

Bifunctional Iminophosphorane Catalyzed Enantioselective Ketimine Phospha-Mannich Reaction

Authors

Gerard P. Robertson

The Department of Chemistry, Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA, UK Email: darren.dixon@chem.ox.ac.uk
Alistair J. M. Farley

The Department of Chemistry, Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA, UK Email: darren.dixon@chem.ox.ac.uk
Darren J. Dixon*

The Department of Chemistry, Chemistry Research Laboratory, University of Oxford, 12 Mansfield Road, Oxford OX1 3TA, UK Email: darren.dixon@chem.ox.ac.uk

Abstract

All articles of this category

Dedicated to Professor Steven V. Ley on the occasion of his 70^th birthday

Abstract

The enantioselective phospha-Mannich reaction of diethyl phosphite to unactivated N-DPP-protected ketimines catalyzed by a bifunctional iminophosphorane (BIMP) superbase organocatalyst is described. The reaction is applicable to ketimines bearing electron-rich and electron-poor aryl substituents and occurs with excellent yields and moderate enantioselectivities under mild reaction conditions.

Key words

asymmetric catalysis - bifunctional organocatalysis - phospha-Mannich - ketimine - superbase

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References

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13 Representative Procedure for the Enantioselective Ketimine Phospha-Mannich Reaction: To a solution of ketimine 2a (128 mg, 0.40 mmol, 2.0 equiv) and catalyst 1b (15 mg, 0.020 mmol, 0.10 equiv in 4.0 mL of diethyl ether) was added diethyl phosphite 3 (26 μL, 0.20 mmol, 1.0 equiv) at rt. Stirring was maintained for 24 h whereupon the crude reaction mixture was purified directly by flash column chromatography [petroleum ether to petroleum ether–EtOAc (1:2), EtOAc then EtOAc–MeOH (9:1)] to afford the phospha-Mannich addition product 4a. Diethyl {(1S)-1-[(Diphenylphosphoryl)amino]-1-phenylethyl}-phosphonate (4a): The title compound 4a was isolated in 99% yield (91 mg) and 58% ee as a colorless solid. ¹H NMR (500 MHz, CDCl₃): δ = 1.03 (t, J = 7.0 Hz, 3 H), 1.25 (t, J = 7.0 Hz, 3 H), 1.82 (d, J _PH = 17.0 Hz, 3 H), 3.53 (ddq, J = 10.0, 7.0, 7.0 Hz, 1 H), 3.81 (ddq, J = 10.0, 7.0, 7.0 Hz, 1 H), 4.03–4.20 (m, 3 H), 7.18–7.30 (m, 5 H), 7.31–7.47 (m, 4 H), 7.51 (dd, J = 7.5, 1.5 Hz, 2 H), 7.55–7.64 (m, 2 H), 7.82–7.91 (m, 2 H). ³¹P NMR (162 MHz, CDCl₃): δ = 20.1 (J _PP = 29.3 Hz), 24.8 (J _PP = 29.3 Hz). HRMS: (ESI⁺): m/z calcd for C₂₄H₂₉NNaO₄P₂: 480.1464; found: 480.1454. See Supporting Information for full characterization data.

Supplementary Material

Supporting Information (PDF)