Synthesis of Chiral o-Aminobenzylamines by Stereoselective Addition of Grignard Reagents to N-[(o-Aminophenyl)methylene] sulfinamides

Abstract

Chiral o-aminobenzylamines are synthons for many chiral ligands and catalysts that have been widely used in asymmetric synthesis. Here, we report a highly efficient and stereoselective addition of Grignard reagents to N-[(o-aminophenyl)methylene]sulfinamides to give a range of o-aminosulfinylimines in good yields with good to excellent diastereoselectivities.

Key words

diamines - aminobenzylamines - sulfinamides - Grignard reagents - stereoselectivity

Publication History

Received: 04 March 2021

Accepted: 10 March 2021

Accepted Manuscript online:
10 March 2021

Article published online:
30 March 2021

• References and Notes

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• 10 Stereoselective Addition of Grignard Reagents to N-[(o-Aminophenyl)methylene]sulfinamides: General Procedure In a 25 mL dry Schlenk tube equipped with a stirring bar, a 1 M solution of the appropriate Grignard reagent 2 in THF (0.6 mmol) was added slowly to a solution of the N-[(o-aminophenyl)methylene]sulfinamide 1 (0.2 mmol) in dry THF (3 mL) at –78 °C. The mixture was stirred at –78 °C until the sulfinamide was consumed (TLC; about 4 h). The mixture was then hydrolyzed with H₂O (10 mL) and diluted with EtOAc. The organic layer was separated and the aqueous phase was extracted with EtOAc (3 × 10 mL). The combined organic phases were dried (MgSO₄), and the solvents were removed in vacuo. Finally, product 3 was purified by flash chromatography. N-[(R)-(2-Aminophenyl)(phenyl)methyl]-2-methylpropane-2-sulfinamide (3a) White solid; yield: 44 mg (72%; dr >20:1); mp 64–65 °C; [α]_D ²⁵ = –18.2 (c 0.33, CHCl₃). ¹H NMR (400 MHz, CDCl₃): δ = 7.44–7.35 (m, 4 H), 7.32–7.28 (m, 1 H), 7.23–7.21 (m, 1 H), 7.16–7.12 (m, 1 H), 6.82–6.78 (m, 1 H), 6.72–6.70 (m, 1 H), 5.74 (d, J = 4.4 Hz, 1 H), 3.99 (d, J = 4.4 Hz, 1 H), 3.47 (br s, 2 H), 1.27 (s, 9 H). ¹³C NMR (100 MHz, CDCl₃): δ = 144.2, 141.0, 129.3, 128.8, 128.7, 127.8, 127.5, 125.7, 118.8, 117.2, 57.9, 56.1, 22.7.

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