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67651237963
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Typical Procedure for the Synthesis of (Z)-Ethyl 2-(Tetrahydrothiazolo[4,3-b][1,3]thiazin-6 (2H, ylidene)acetate (9f) The thioester 7f (50.5 mg, 0.17 mmol) was dissolved in dry EtOH (5 mL) and a solution of NaOEt (0.2 M in EtOH, 0.85 mL, 0.17 mmol) was added at r.t. with vigorous stirring. After hydrolysis to thiol, as evidenced by complete consumption of the reactant (ca. 15 min; TLC, the reaction mixture was cooled down to 0°C. Twofold mass excess of NaBH 4 (101 mg, 15-20 mmol equiv) was added, followed by 3 drops of 0.4 M HCl in EtOH. The addition of the same amount of acid was continued in regular 10 min intervals until the end of the reaction 45 min, when the reaction mixture was quenched with 1 M HCl in EtOH. The suspension was stirred for an additional 30 min at 0°C, diluted with H2O, extracted with CHCl 3, the organic phase separated, dried with Na2SO 4
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+ calcd: 246.06170; found: 246.06176 ± 0.24 ppm.
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-
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32
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67651239989
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Analytical Data of (Z)-Ethyl 2-{7-Methyl-2H-thiazolo[4,3- b]thiazol-5 (3H,7H,7aH)-ylidene}acetate (9c) Isolated in 37% yield as a mixture of trans- and cis-isomer in a 75:25 ratio. Compound trans-9c: 1H NMR (500 MHz, CDCl3, δ, 1.26 (3 H, t, J, 7.0 Hz, CH 3CH2, 1.49 (3 H, d, J, 6.5 Hz, CH 3CHS, 3.09-3.12 (1 H, m, CH2S, 3.15-3.20 (1 H, m, CH2S, 3.26-3.32 (1 H m, CH2N, 3.66 (1 H, dq, J1, 6.5 Hz, J2, 5.5 Hz, CHCH3S, 3.97 (1 H, ddd, J1, 9.0 Hz, J2, 6.0 Hz, J3, 3.0 Hz, CH2N) 4.16 (2 H, q, J, 7.0 Hz, CH2CH3, 4.89 (1 H, d, J, 5.5 Hz, CHSN, 5.07 (1 H, s, CH) ppm. 13C NMR 50.3 MHz, CDCl3
-
3), 76.8 (CHSN), 84.8 (=CH), 163.8 (C=), 168.6 ppm.
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-
-
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33
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34548150214
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For recent examples of the 5-endo-trig mode ring-closing reaction, see: (a) Fuwa, H.; Sasaki, M. Org. Lett. 2007, 9, 3347.
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For recent examples of the 5-endo-trig mode ring-closing reaction, see: (a) Fuwa, H.; Sasaki, M. Org. Lett. 2007, 9, 3347.
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