Enantioselective Synthesis of α-Chiral Amides by Catalytic Hydrogenation with Iridium N,P-Complexes

Bram B. C. Peters; Norman Birke; Luca Massaro; Pher G. Andersson

doi:10.1055/s-0042-1751399

Synlett, Table of Contents

Synlett 2023; 34(12): 1519-1523
DOI: 10.1055/s-0042-1751399

cluster

Special Issue Honoring Masahiro Murakami’s Contributions to Science

Enantioselective Synthesis of α-Chiral Amides by Catalytic Hydrogenation with Iridium N,P-Complexes

Bram B. C. Peters ‡

^aDepartment of Organic Chemistry, Stockholm University, Svante Arrhenius väg 16C, 10691 Stockholm, Sweden

,

Norman Birke‡

^aDepartment of Organic Chemistry, Stockholm University, Svante Arrhenius väg 16C, 10691 Stockholm, Sweden

,

Luca Massaro

^aDepartment of Organic Chemistry, Stockholm University, Svante Arrhenius väg 16C, 10691 Stockholm, Sweden

,

Pher G. Andersson∗

^aDepartment of Organic Chemistry, Stockholm University, Svante Arrhenius väg 16C, 10691 Stockholm, Sweden

^bSchool of Chemistry and Physics, University of Kwazulu-Natal, Private Bag X54001, 4000 Durban, South Africa

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Abstract

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Abstract

The catalytic asymmetric hydrogenation of olefins constitutes a powerful method for the preparation of chiral compounds. A series of prochiral unsaturated amides were efficiently reduced with high enantioselectivities by means of an iridium N,P-complex-catalyzed hydrogenation. Its application in the synthesis of fenpropidin and the possibility of using isomeric mixtures of starting materials are attractive features of the method.

Key words

amides - enantioselectivity - iridium catalysis - asymmetric catalysis - hydrogenation

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References

References and Notes

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19 α,β-Unsaturated Amides 1; General Procedure The appropriate α,β-unsaturated carboxylic acid (10.0 mmol, 1.00 equiv) was refluxed in SOCl₂ (5 mL) for 1 h, after which excess SOCl₂ was evaporated in vacuo. The resulting acyl chloride was redissolved in anhydrous CH₂Cl₂ (20 mL), and the solution was cooled to 0 °C. The appropriate amine (20.0 mmol, 2.00 equiv) and Et₃N (5.60 mL, 40.0 mmol, 4.00 equiv) were added, and the mixture was stirred overnight at room temperature. Sat. aq NH₄Cl (20 mL) was then added to quench the reactants, and the mixture was extracted with Et₂O (3 × 20 mL). The combined organic phases were washed with brine (20 mL), dried (Na₂SO₄), and evaporated to dryness in vacuo to give the crude product. This was purified by column chromatography [silica gel, pentane–Et₂O (60:40)] to give the desired α,β-unsaturated amide. This was filtered over basic Al₂O₃, eluting with pentane–Et₂O (60:40), immediately before hydrogenation.
20 4-[(2E)-2-methyl-3-phenylprop-2-enoyl]morpholine (1b) Synthesized, by following the general procedure, from (2E)-2-methyl-3-phenylacrylic acid (0.81 g, 5.0 mmol), morpholine (0.87 mL, 10.0 mmol), and Et₃N (2.8 mL, 20.0 mmol) as a colorless oil; yield: 0.94 g (4.1 mmol, 82%). ¹H NMR (400 MHz, CDCl₃): δ = 7.41–7.27 (m, 5 H), 6.54 (q, J = 1.7 Hz, 1 H), 3.75–3.69 (m, 4 H), 3.66 (m, 4 H), 2.11 (d, J = 1.6 Hz, 3 H). The spectroscopic data were in agreement with the reported values.^23a
21 Asymmetric Hydrogenation of α,β-Unsaturated Amides An oven-dried vial was charged with the appropriate unsaturated amide (0.1 mmol, 1.0 equiv) and Ir-N,P catalyst (1.0 mol%). Freshly distilled toluene (0.5 mL) and a magnetic stirring bar were added, and the vial was placed in a high-pressure hydrogenation apparatus. The reactor was purged three times with Ar and three times with H₂, then pressurized with H₂ (10 bar). The mixture was stirred at rt for 16 h before the H₂ pressure was released and the solvent was removed under reduced pressure. The residue was purified by flash chromatography [silica gel, pentane–Et₂O (25:75)] to give the chiral alkane. The enantioselectivity was determined by GC or SFC analysis on a chiral stationary phase. The corresponding racemic product, used for comparison, was prepared on a 0.05 mmol scale by using Pd/C or a racemic Ir catalyst, following the same hydrogenation procedure. The absolute configuration was determined by comparing the sign of the optical rotation with the reported value.
22 4-(2-Methyl-3-phenylpropanoyl)morpholine (2b) Prepared, by following the general procedure, from 1b (23.1 mg, 0.1 mmol) in the presence of catalyst F as a colorless oil; yield: 23.1 mg (0.99 mmol, 99%); [α]_D ²⁶ +35.0 (c 0.1 M, CHCl₃). ¹H NMR (400 MHz, CDCl₃): δ = 7.32–7.24 (m, 3 H), 7.18–7.13 (m, 2 H), 3.74–3.54 (m, 2 H), 3.50–3.41 (m, 3 H), 3.35–3.25 (m, 1 H), 3.20–3.10 (m, 1 H), 3.05–3.00 (m, 1 H), 3.00–2.89 (m, 2 H), 2.75–2.64 (m, 1 H), 1.18 (d, J = 6.4 Hz, 3 H). The spectroscopic data were in agreement with the reported values.^23b

23a Hayashi C, Hayashi T, Yamada T. Bull. Chem. Soc. Jpn. 2015; 88: 862
23b Banerjee A, Hattori T, Yamamoto H. Synthesis 2023; in press

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