Facile Preparation of Highly Enantioenriched 1,4-Benzothiazin-3-ones by the Substitution of α-Bromoacetate with 2-Aminothiophenol

Abstract

A simple and convenient approach for highly enantioenriched 2-substituted 1,4-benzothiazin-3-ones was developed via the nucleophilic substitution of α-bromoacetates derived from either l-threonate or l-serinate using 2-aminothiophenol and a subsequent facile lactamization.

Key words

1,4-benzothiazin-3-one - carbon–sulfur bond formation - dynamic resolution - asymmetric synthesis - chiral auxiliaries - lactamization

Publication History

Received: 23 October 2022

Accepted after revision: 27 December 2022

Accepted Manuscript online:
27 December 2022

Article published online:
23 January 2023

• References and Notes

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• 9 The absolute configurations of 1,4-benzothiazin-3-ones were assigned by assuming an inversion of stereochemistry in the reaction of α-bromoacetates (αR)-1c–e or (αS)-11a,b. The occurrence of an S_N2-type mechanism has been observed in the substitution of α-bromoacetates with various N-, O-, and S-nucleophiles.^6–8
• 10 General Procedure for the Preparation of 1,4-Benzothiazin-3(4H)-ones 2-Aminothiophenol (1.5 equiv) and Et₃N (1.0 equiv) were added to a solution of α-bromoacetate (1.0 mmol) in CH₂Cl₂ (ca. 0.1 M) at room temperature. The reaction mixture was stirred at room temperature for 0.5 h, then trifluoroacetic acid (TFA, 3.0 equiv) was added. After stirring for 10 min, ethyl acetate was added for dilution. The resulting mixture was washed with saturated NaHCO₃ solution, dried with anhydrous MgSO₄, filtered, concentrated, and purified by column chromatography to afford a product. 2-(n-Butyl)-6-chloro-1,4-benzothiazin-3(4H)-one (20) A yellow oil was obtained in 73% yield from 11b. ¹H NMR (400 MHz, CDCl₃): δ = 10.1 (s, 1 H), 7.23–6.97 (m, 3 H), 3.41–3.38 (m, 1 H), 1.91–1.87 (m, 1 H), 1.60–1.54 (m, 2 H), 1.36–1.31 (m, 3 H), 0.91–0.87 (m, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 169.1, 137.0, 132.6, 129.1, 123.9, 117.1, 117.0, 42.5, 29.5, 28.8, 22.1, 13.9. HRMS: m/z calcd for C₁₂H₁₅ClNOS [M⁺ + 1]: 256.0563; found: 256.0563. Chiral HPLC: 99:1 er, t_R (major enantiomer) = 18.3 min; t_R (minor enantiomer) = 14.9 min (Chiralcel OD column; 10% 2-propanol in hexane; 0.5 mL/min).
• 11 We also found that the CIDR of α-ethyl- or α-n-hexyl-substituted α-bromoacetate derived from N-benzoyl-l-serine isopropyl ester gave ca. 81:19 dr under the same CIDR conditions.