Unexpected Highly Efficient Ring-Opening of Aziridines or Epoxides with Iodine Promoted by Thiophenol

Jie Wu; Xiaoyu Sun; Wei Sun; Shengqing Ye

doi:10.1055/s-2006-950417

LETTER

Unexpected Highly Efficient Ring-Opening of Aziridines or Epoxides with Iodine Promoted by Thiophenol

Jie Wu*^a,b, Xiaoyu Sun^a, Wei Sun^a, Shengqing Ye^a
^a Department of Chemistry, Fudan University, 220 Handan Road, Shanghai 200433, P. R. of China
Fax: +86(21)65102412; e-Mail: jie_wu@fudan.edu.cn;
^b State Key Laboratory of Organometallic Chemistry, Shanghai Institute of Organic Chemistry, Chinese Academy of Sciences, 354 Fenglin Road, Shanghai 200032, P. R. of China

Abstract

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Abstract

Ring-opening of aziridines or epoxides with iodine promoted by thiophenol afforded β-iodo amines or β-iodo alcohols in good to excellent yields under mild reaction conditions with extremely high efficiency.

Key words

aziridine - epoxide - iodine - thiophenol - ring-opening

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References

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General Procedure for the Reactions of Aziridines 1 or Epoxide 4 with Iodine Promoted by Benzenethiol
Benzenethiol (1.0 equiv) was added to a solution of aziri-dines 1 or epoxide 4 (0.30 mmol) and iodine (0.15 mmol) in CH₂Cl₂ (2.0 mL). The reaction mixture was stirred at r.t. (open to air). After the reaction was completed in 1 min, the mixture was purified directly by flash column chromatog-raphy on silica gel afforded the corresponding product.
Data of New Compounds
N-(2-Iodocycloheptyl)-4-methylbenzenesulfonamide (2c): ¹H NMR (400 MHz, CDCl₃): δ = 1.41-1.69 (m, 7 H), 1.95-2.10 (m, 3 H), 2.43 (s, 3 H), 3.63-3.64 (m, 1 H), 4.25-4.27 (m, 1 H), 5.35 (d, J = 6.8 Hz, 1 H), 7.31 (d, J = 7.8 Hz, 2 H), 7.80 (d, J = 8.3 Hz, 2 H) ppm. ¹³C NMR (100 MHz, CDCl₃): d = 21.6, 22.4, 26.0, 27.2, 31.6, 36.0, 38.6, 63.0, 127.5, 129.7, 137.0, 143.6 ppm. MS: m/z = 393 [M⁺]. HRMS: m/z calcd for C₁₄H₂₀INO₂S: 393.0259; found: 393.0264.
N-(1-Iodooctadecan-2-yl)-4-methylbenzenesulfonamide-(2j): ¹H NMR (400 MHz, CDCl₃): δ = 0.87 (t, J = 6.4 Hz, 3 H), 1.12-1.42 (m, 30 H), 2.43 (s, 3 H), 2.92-3.01 (m, 1 H), 3.14-3.25 (m, 2 H), 4.89 (d, J = 8.3 Hz, 1 H), 7.30 (d, J = 8.3 Hz, 2 H), 7.79 (d, J = 8.3 Hz, 2 H) ppm. ¹³C NMR (100 MHz, CDCl₃): d = 14.1, 14.7, 21.5, 22.7, 25.2, 28.7, 29.0, 29.2, 29.4, 29.5, 29.7, 31.9, 35.5, 52.6, 127.1, 129.8, 137.9, 143.6 ppm. MS: m/z = 549 [M⁺]. HRMS: m/z calcd for C₂₅H₄₄INO₂S: 549.2137; found: 549.2132.
N-(2-Iodooctadecyl)-4-methylbenzenesulfonamide (3j): ¹H NMR (400 MHz, CDCl₃): δ = 0.87 (t, J = 6.4 Hz, 3 H), 1.20-1.42 (m, 30 H), 2.43 (s, 3 H), 3.20-3.24 (m, 2 H), 3.98-4.01 (m, 1 H), 5.12 (t, J = 6.4 Hz, 1 H), 7.30 (d, J = 8.3 Hz, 2 H), 7.79 (d, J = 8.3 Hz, 2 H) ppm. ¹³C NMR (100 MHz, CDCl₃): d = 14.1, 14.7, 21.5, 22.7, 25.2, 28.7, 29.0, 29.2, 29.4, 29.5, 29.7, 31.9, 35.5, 52.6, 127.1, 129.8, 137.9, 143.6 ppm. MS: m/z = 549 [M⁺]. HRMS: m/z calcd for C₂₅H₄₄INO₂S: 549.2137; found: 549.2132.
N-(1-Iodo-1-phenylpropan-2-yl)-4-methylbenzenesulfona-mide (anti-2k): ¹H NMR (400 MHz, CDCl₃): δ = 1.16 (d, J = 6.4 Hz, 3 H), 2.42 (s, 3 H), 3.06-3.10 (m, 1 H), 4.92 (d, J = 8.8 Hz, 1 H), 5.15 (d, J = 4.4 Hz, 1 H), 7.21-7.35 (m, 7 H), 7.73 (d, J = 8.3 Hz, 2 H) ppm.
N-(1-Iodo-1-phenylpropan-2-yl)-4-methylbenzenesulfona-mide (syn- 2k): ¹H NMR (400 MHz, CDCl₃): δ = 1.14 (d, J = 6.4 Hz, 3 H), 2.38 (s, 3 H), 3.59-3.60 (m, 1 H), 4.80 (d, J = 8.3 Hz, 1 H), 5.05 (d, J = 5.8 Hz, 1 H), 7.21-7.35 (m, 7 H), 7.73 (d, J = 8.3 Hz, 2 H) ppm. MS: m/z = 415 [M⁺]. HRMS: m/z calcd for C₁₆H₁₈INO₂S: 415.0103; found: 415.0106.