One-step, Enantiospecific Transformationof Cyclic, Five-membered-1,2-diols into their Respective 1,2-Bis(phenylsulfanyl)Derivatives

Jacek Skarżewski; Anil Gupta; Elżbieta Wojaczyńska; Renata Siedlecka

doi:10.1055/s-2003-41015

LETTER

One-step, Enantiospecific Transformationof Cyclic, Five-membered-1,2-diols into their Respective 1,2-Bis(phenylsulfanyl)Derivatives

Jacek Skarżewski*, Anil Gupta, Elżbieta Wojaczyńska, Renata Siedlecka
Institute of Organic Chemistry, Biochemistryand Biotechnology, Wrocaw University of Technology, 50-370 Wrocaw, Poland
Fax: +48(71)3284064; e-Mail: skarzewski@kchf.ch.pwr.wroc.pl;

Abstract

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Abstract

The enantiomeric cyclic, five-membered vic-diolsreacted with (PhS)₂/Bu₃P in benzeneat 80 °C giving the corresponding bis(phenylsulfanyl) derivatives(42-74%) with complete inversion of configurationat both stereogenic centers. Similar reaction conditions were alsosuccessfully used for the enantiospecific transformation of a singlehydroxy group into the respective enantiomeric thioether function.For other vic-diols the neighboring groupparticipation hampered the stereoselectivity of the double substitution.

Key words

diols - stereoselective synthesis - Mitsunobureaction - thioethers

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References

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General Procedurefor the Preparation of Bis(sulfides): A solution of diol (0.8mmol), PhSSPh (1.05g, 4.8 mmol) and Bu₃P (1.59 mL, 6.4mmol) in dry benzene (5 mL) was placed under argon in a reactionampule. The sealed tube was heated at 80 °C for three days.Thereafter the cooled mixture was diluted with Et₂O (20mL), washed with 2 M NaOH, brine and dried over anhyd Na₂SO₄.After evaporation, the crude product was purified by chromatographyon silica gel. Selected data for the obtained products are givenbelow.

(1R,2R)-2a: crystallizingoil. ¹H NMR (CDCl₃): δ = 1.71-1.77(m, 2 H, CH₂), 1.83-1.93 (m, 2 H, CH_aH_b),2.31-2.43 (m, 2 H, CH_aH_b), 3.58 (dd,2 H, J ₁ = 5.3Hz, J ₂ = 2.4Hz, CHS), 7.24 (s, 10 H, Ar). ¹³C NMR(CDCl₃): δ = 23.16, 30.94, 52.74, 126.72,128.90, 131.26, 135.46. IR (film): 3073, 3058, 3019, 3003, 2960,2865, 1583, 1480, 1438, 1091, 1025, 909, 736, 691 cm^-1.MS (EI, 70 eV): m/z (%) = 286(4.3) [M⁺], 177 (69) [M⁺ - PhS],135(9) [PhSCH=CH⁺], 109(25) [PhS⁺], 67 (100) [C₅H₇ ⁺].(3R,4R)-2b: mp 62-63 °C (MeOH). ¹HNMR (CDCl₃): δ = 3.68 (dd, 2 H, J ₁ = 4.2Hz, J ₂ = 3.0Hz, CHS), 3.83 (dd, 2 H, J ₁ = 9.6Hz, J ₂ = 3.0Hz, CH_aH_b), 4.34 (dd, J ₁ = 9.5Hz, J ₂ = 5.4Hz, CH_aH_b), 7.24 (s, 10 H, Ar). ¹³CNMR (CDCl₃): δ = 52.14, 72.25, 127.37, 129.15,131.67, 134.05. IR (KBr): 3049, 2952, 2926, 2873, 1580, 1482, 1469,1438, 1065, 894, 749, 697, 689 cm^-1.MS (EI, 70 eV): m/z (%) = 288(4) [M⁺], 179 (40) [M⁺ - PhS], 135(23) [PhSCH=CH⁺],109 (68) [PhS⁺], 69 (100) [C₄H₅O⁺].(+)-(3R,4R)-2c: from (+)-(3S,4S)-1c: mp 58-59 °C. [α]_D ²⁰ +54.0(c 1.00, CH₂Cl₂, >98% ee), {Lit.^2a (+)-(3R,4R)-2c: [α]_D ²⁰ +52.7(c 0.55, CHCl₃)}.UV/Vis (CH₃CN): λ_max (log ε) = 216nm (3.84), 256 nm (3.67). CD (CH₃CN): λ (Δε) = 229(-1.4), 243(0), 258 (+1.1). MS (EI, 70 eV): m/z (%) = 377(2) [M⁺], 268 (75) [M⁺ - PhS],149 (100) [PhSCH=CH-CH₂ ⁺],116(11) [C₅H₁₀NS⁺],91 (51) [C₇H₇ ⁺].(-)-(3S,4S)-2c: mp 58-59 °C. [α]_D ²⁰ -54.0(c 1.16, CH₂Cl₂).(3R,4R)-2d: mp 49-51 °C (MeOH). ¹HNMR (CDCl₃): δ = 0.87 (t, 3 H, CH₃),1.25 (m, 18 H, CH₂), 1.55 (m, 2 H, CH₂), 2.41(m, 2 H, CH₂), 2.68 (m, 2 H, CH₂), 3.24 (m,2 H, CH₂), 3.63 (t, 2 H, NCH₂), 7.24-7.40(m, 10 H, ArH). ¹³C NMR (CDCl₃): δ = 14.11,22.68, 24.21, 27.30, 29.33, 29.39, 29.52, 29.57, 29.62, 30.19, 31.90,51.05, 56.53, 59.18, 127.26, 129.11, 131.54, 134.45. IR (KBr): 3058,2925, 2853, 1584, 1480, 738, 690 cm^-1.MS (EI, 70 eV): m/z (%) = 149(100) [PhSCH=CH-CH₂ ⁺],116(13) [C₅H₁₀NS⁺],82(42) [C₅H₈N⁺].(3R,4R)-6: Obtained by the usual procedure using:(+)-(3S,4S)-1c (1 equiv), (2-NaphthS)₂ (3equiv) and Bu₃P (4 equiv) in dry benzene. Yield 88%.Mp 98-100 °C (CH₂Cl₂-hexane).R_f = 0.45 (n-hexane/EtOAC9:1): [α]_D ²⁰ +108.2(c 0.78, CH₂Cl₂). ¹H NMR(CDCl₃): δ = 2.73 (dd, 2 H, J ₁ = 10.3Hz, J ₂ = 3.9Hz), 3.21-3.31 (m, 2 H), 3.65 and 3.79 (q, 2 H, J _AB = 13.7Hz,, AB-system, CH₂Ph), 3.79-3.83 (m, 2 H),6.98-7.74 (m, 19 H, ArH). ¹³CNMR (CDCl₃): δ = 52.57, 59.69, 59.98,126.42, 126.87, 127.50, 127.71, 128.05, 128.74, 128.84, 128.96, 129.15,130.29, 132.53, 132.86, 133.98, 138.82. IR (KBr): 3050, 2961, 1727,1271, 1130, 819, 740 cm^-1. MS (EES,4.5 kV): m/z = 478.7 [M + H]⁺.

(3S,4R)-3: Obtainedby the usual procedure using: (+)-(3S,4S)-1c (1 equiv),PhSSPh (1.5 equiv) and Bu₃P (2 equiv) in dry benzene.Mp 66-67 °C (EtOH). ¹H NMR(CDCl₃): δ = 2.15-2.62(m, 2 H, CH₂), 2.82 (br s, 1 H, OH), 3.05-3.11 (m,2 H, CH₂), 3.66 (s, 2 H, CH₂), 3.77 (m, 1H, CH-S), 4.30-4.32 (m, 1 H, CH-O), 7.19-7.37(m, 10 H, ArH), cis-vic-methinehydrogens coupling: ³ J = 5.9Hz (decoupling experiment). ¹³C NMR(CDCl₃): δ = 52.51, 58.18, 60.56, 61.76,70.71, 127.21, 127.64, 128.78, 129.20, 129.52, 130.56, 135.63, 138.60.IR (film): 3403, 3060, 3028, 2935, 2802, 1584, 1481, 1438, 1143,1090, 1026, 740, 700 cm^-1. (R)-5: oil. R_f = 0.27(n-hexane/EtOAc 9:1). ¹HNMR (CDCl₃): δ = 1.74-1.78(m, 1 H, H₄), 2.25-2.29 (m, 1 H, H₄), 2.40(dd, 1 H, J ₁ = 9.9Hz, J ₂ = 6.2Hz, H₂), 2.51-2.55 (m, 1 H, H₅),2.61-2.65 (m, 1 H, H₅), 3.01 (dd, 1 H, J ₁ = 9.9Hz, J ₂ = 7.3Hz, H₂), 3.53 and 3.60 (q, 2 H, J _AB = 12.9Hz, AB-system, CH₂Ph), 3.67-3.72 (m, 1 H, H₃),7.07-7.27 (m, 10 H, ArH). ¹³CNMR (CDCl₃): δ = 32.78, 43.47, 53.64,60.54, 61.22, 126.49, 127.44, 128.70, 129.17, 129.28, 130.07, 137.12,139.17. IR(film): 3059, 2959, 2792, 1584, 1480, 1439, 1145, 1026,738, 699 cm^-1. (+)-(1R,3R)-10: oil. R_f = 0.58(n-hexane/EtOAc 10:1). Yield65%. [α]_D ²⁰ +150.0 (c 2.34, CH₂Cl₂, >95% ee). ¹HNMR (CDCl₃): δ = 2.53 (t, 2 H, J = 7.6 Hz,CH₂), 4.01 (t, 2 H, J = 7.6Hz, CH), 7.07-7.27 (m, 20 H, ArH). ¹³CNMR (CDCl₃): δ = 41.95, 50.72, 127.58,127.94, 128.44, 128.95, 129.09, 132.74, 134.81, 140.71.

(1S,3R,S _S)-8 [16] wasdeoxygenated [15] to (1S,3R)-9 in 71% yield. R_f = 0.64(t-BuOMe/CHCl₃/n-hexane, 2.5:2:7). [α]_D ²⁰ +127.1(1.88, CH₂Cl₂, >95% ee). ¹HNMR (CDCl₃): δ = 1.85 (d, 1 H, -OH, J = 3.5 Hz),2.13-2.19 (m, 1 H, CH₂), 2.35-2.41(m, 1 H, CH₂), 4.35 (dd, 1 H, CH-S, J ₁ = 9.8Hz, J ₂ = 5.6Hz), 4.48 (dt, 1 H, CH-O, J ₁ = 9.5Hz, J ₂ = 3.6Hz), 6.91-7.23 (m, 15 H, ArH). ¹³CNMR (CDCl₃): δ = 45.47, 50.55, 72.46,126.13, 127.58, 127.73, 128.16, 128.39, 128.92, 128.96, 129.11,132.86, 134.89, 141.77, 144.65.