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Synlett 2021; 32(10): 1019-1023
DOI: 10.1055/a-1423-5679
DOI: 10.1055/a-1423-5679
letter
Synthesis of Chiral o-Aminobenzylamines by Stereoselective Addition of Grignard Reagents to N-[(o-Aminophenyl)methylene] sulfinamides
We thank the National Natural Science Foundation of China (No. 22001093) and the Fundamental Research Funds for the Central Universities (21620354) for financial support.
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.
Supporting Information
- Supporting information for this article is available online at https://doi.org/10.1055/a-1423-5679.
- Supporting Information
Publication History
Received: 04 March 2021
Accepted: 10 March 2021
Accepted Manuscript online:
10 March 2021
Article published online:
30 March 2021
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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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For reviews on the chemistry of N-tert-butanesulfinyl imines, see:
For selected reviews on catalytic asymmetric Friedel−Crafts alkylation reactions, see: