Synlett 2017; 28(04): 429-432
DOI: 10.1055/s-0036-1588377
letter
© Georg Thieme Verlag Stuttgart · New York

Cascade Thiol-Michael–Aldol Reaction Promoted by Tetramethyl Guanidine: Synthesis of 2H-Thiochromene-3-carboxylate Libraries

Thi Thu Huong Nguyen
a  Medicinal Chemistry Laboratory, Faculty of Chemistry, VNU-HUS, 19 Le Thanh Tong, Hoan Kiem, Ha Noi, Vietnam   Email: macdinhhung@hus.edu.vn
,
Thi Xuyen Nguyen
a  Medicinal Chemistry Laboratory, Faculty of Chemistry, VNU-HUS, 19 Le Thanh Tong, Hoan Kiem, Ha Noi, Vietnam   Email: macdinhhung@hus.edu.vn
,
Thi Thuong Thuong Cao
a  Medicinal Chemistry Laboratory, Faculty of Chemistry, VNU-HUS, 19 Le Thanh Tong, Hoan Kiem, Ha Noi, Vietnam   Email: macdinhhung@hus.edu.vn
,
Tuan Hoang Dinh
a  Medicinal Chemistry Laboratory, Faculty of Chemistry, VNU-HUS, 19 Le Thanh Tong, Hoan Kiem, Ha Noi, Vietnam   Email: macdinhhung@hus.edu.vn
,
Hung Huy Nguyen
b  Faculty of Chemistry, VNU-HUS, 19 Le Thanh Tong, Hoan Kiem, Ha Noi, Vietnam
,
Thai Thanh Thu Bui
b  Faculty of Chemistry, VNU-HUS, 19 Le Thanh Tong, Hoan Kiem, Ha Noi, Vietnam
c  Group ‘Medicinal Chemistry and Applied Natural Product’, Faculty of Chemistry, VNU-HUS, 19 Le Thanh Tong, Hoan Kiem, Ha Noi, Vietnam
,
Van Phong Pham
b  Faculty of Chemistry, VNU-HUS, 19 Le Thanh Tong, Hoan Kiem, Ha Noi, Vietnam
c  Group ‘Medicinal Chemistry and Applied Natural Product’, Faculty of Chemistry, VNU-HUS, 19 Le Thanh Tong, Hoan Kiem, Ha Noi, Vietnam
,
Dinh Hung Mac*
a  Medicinal Chemistry Laboratory, Faculty of Chemistry, VNU-HUS, 19 Le Thanh Tong, Hoan Kiem, Ha Noi, Vietnam   Email: macdinhhung@hus.edu.vn
c  Group ‘Medicinal Chemistry and Applied Natural Product’, Faculty of Chemistry, VNU-HUS, 19 Le Thanh Tong, Hoan Kiem, Ha Noi, Vietnam
› Author Affiliations
Further Information

Publication History

Received: 16 October 2016

Accepted after revision: 15 November 2016

Publication Date:
08 December 2016 (eFirst)

Abstract

Tetramethylguanidine (TMG) promotes a cascade thiol-­Michael–aldol–dehydration reaction between 2-mercaptobenzaldehyde and cinnamate esters to synthesize 2H-thiochromene-3-carboxylate derivatives. The target thiochromene compounds with a variety of substituents were obtained in high yields.

Supporting Information

 
  • References and Notes

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  • 16 General Procedure A mixture of 2-mercaptobenzaldehyde (1, 55 mg, 0.4 mmol), methyl cinnamate (2, 32 mg, 0.2 mmol), and TMG (25 μL, 0.2 mmol) dissolved in dry toluene (1 mL) was stirred at r.t. for 24 h. After completion of the reaction, the solvent was evaporated under vacuum, and the crude product was purified by chromatography (n-hexane–EtOAc, 80:20) to give a mixture of diastereoisomers 3 as a pale yellow liquid (57 mg, 95 %). This product was then dissolved in toluene (1 mL) with PTSA (36 mg, 0.19 mmol). The mixture was heated at 90 °C for 1 h. After completion of the reaction, the solvent was evaporated under vacuum, and the crude product was purified by chromatography (n-hexane–EtOAc, 95:5) to give compound 4 as a yellow solid (40 mg, 75% after 2 steps). Methyl 2-Phenyl-2H-thiochromene-3-carboxylate (4a) 1H NMR (500 MHz, CDCl3): δ = 7.84 (s, 1 H), 7.25–7.15 (m, 5 H), 7.08 (t, J = 7.9 Hz, 1 H), 7.01 (dd, J = 7.6, 0.8 Hz, 1 H), 6.81 (dd, J = 8.1, 0.9 Hz, 1 H), 5.23 (s, 1 H), 4.10–3.91 (m, 2 H), 3.78 (s, 3 H), 1.38 (t, J = 7.0 Hz, 3 H). 13C NMR (126 MHz, CDCl3): δ = 165.38, 153.84, 141.53, 136.03, 129.92, 127.51, 126.51, 125.70, 124.18, 123.72, 122.14, 120.57, 112.61, 63.50, 51.23, 38.56, 13.64. HRMS: m/z calcd for [M + Na]+ C17H14NaO2S: 305.0612; found: 305.0615.