Diastereoselective Synthesis of Enantiomerically Pure 1,2-Disubstituted Cyclopropanols from Allylic Sulfones

D. Diez; P. García; M. P. Pacheco; I. S. Marcos; N. M. Garrido; P. Basabe; J. G. Urones

doi:10.1055/s-2002-19749

LETTER

Diastereoselective Synthesis of Enantiomerically Pure 1,2-Disubstituted Cyclopropanols from Allylic Sulfones

D. Diez*, P. García, M. P. Pacheco, I. S. Marcos, N. M. Garrido, P. Basabe, J. G. Urones
Dpto. de Química Orgánica, Universidad de Salamanca, Plaza de los Caídos 1-5, 37008 Salamanca, Spain
Fax: +34(923)294574; e-Mail: ddm@usal.es;

Abstract

All articles of this category

Abstract

Enantiomerically pure 1,2-disubstituted cyclopropanols have been obtained from allylic sulfones derived from (R)-glyceraldehyde, in good yield.

Key words

cyclopropanols - sulfones - cyclization - synthesis

Full Text

References

<A NAME="RD23601ST-1A">1a</A> Donaldson WA. Tetrahedron 2001, 57: 8589 ; and references cited therein

<A NAME="RD23601ST-1B">1b</A> Esposito A. Taddei M. J. Org. Chem. 2000, 65: 9245

For leading references, see:

<A NAME="RD23601ST-2A">2a</A> Salaün J. Rappoport Z. In The Chemistry of the Cyclopropyl Group, Rearrangements Involving the Cyclopropyl Group Wiley; New York: 1987. p.809

<A NAME="RD23601ST-2B">2b</A> Houben-Weyl: Methods of Organic Chemistry, Carbocyclic Three and Four-membered Ring Systems Vol. E.17: de Meijere A. Thieme Verlag; Stuttgart: 1997.

<A NAME="RD23601ST-2C">2c</A> Sylvestre I. Olivier J. Salaün J. Tetrahedron Lett. 2001, 42: 4991 ; and references cited therein

<A NAME="RD23601ST-2D">2d</A> Shaffer CL. Morton MD. Hanzlik RP. J. Am. Chem. Soc. 2001, 123: 8502

<A NAME="RD23601ST-2E">2e</A> Kulinkovich OG. de Meijere A. Chem. Rev. 2000, 100: 2789 ; and references cited therein

For asymmetric synthesis of 1,2-disubstituted cyclopropanols in enantiomerically pure form from boronic esters, see:

<A NAME="RD23601ST-3A">3a</A> Pietruszka J. Widenmeyer M. Synlett 1997, 977

<A NAME="RD23601ST-3B">3b</A> Fontani P. Carboni B. Vaultier M. Maas G. Synthesis 1991, 605

<A NAME="RD23601ST-3C">3c</A> Imai T. Mineta H. Nishida S. J. Org. Chem. 1990, 55: 4986

<A NAME="RD23601ST-3D">3d</A> Pietruszka J. Witt A. J. Chem. Soc. Perkin Trans. 1 2000, 4293

<A NAME="RD23601ST-3E">3e</A> Luithle JEA. Pietruszka J. Witt A. J. Chem. Soc., Chem. Commun. 1998, 2651

<A NAME="RD23601ST-3F">3f</A> Taylor RE. Schmidt MJ. Yuan H. Org. Lett. 2000, 2: 601 ; and references cited therein

<A NAME="RD23601ST-3G">3g</A> Baird MS. Huber AM. Clegg W. Tetrahedron 2001, 57: 9849

<A NAME="RD23601ST-4">4</A> McGaffin G. Grimm B. Heinecke U. Michaelsen H. de Meijere A. Walsh R. Eur. J. Org. Chem. 2001, 3559 ; and references cited therein

<A NAME="RD23601ST-5A">5a</A> Morikawa T. Saski H. Hanai R. Shibuya A. Taguchi T. Muray E. J. Org. Chem. 1994, 59: 97

<A NAME="RD23601ST-5B">5b</A> Evans DA. Burch JD. Org. Lett. 2001, 3: 503

<A NAME="RD23601ST-5C">5c</A> Alvarez-Larena A. Piniella JF. Branchadell V. Ortuño RM. J. Org. Chem. 2000, 65: 388

<A NAME="RD23601ST-5D">5d</A> Ma D. Cao Y. Yang Y. Cheng D. Org. Lett. 1999, 1: 285

<A NAME="RD23601ST-6A">6a</A> Urones JG. Marcos IS. Garrido NM. Basabe P. Bastida AJ. San Feliciano SG. Díez Martín D. Goodman JM. Synlett 1998, 1361

<A NAME="RD23601ST-6B">6b</A> Díez Martín D. San Feliciano SG. Marcos IS. Basabe P. Garrido NM. Urones JG. Synthesis 2001, 1069

<A NAME="RD23601ST-7A">7a</A> Urones JG. Díez Martín D. Marcos IS. Garrido NM. Basabe P. San Feliciano SG. Coca R. Synlett 1998, 41: 1364

<A NAME="RD23601ST-7B">7b</A> Díez Martín D. Templo Beneitez M. Marcos IS. Garrido NM. Basabe P. Urones JG. Synlett 2001, 655

<A NAME="RD23601ST-8A">8a</A> Carreño MC. Cid MB. Carcia Ruano JL. Santos M. Tetrahedron Lett. 1998, 39: 1405

<A NAME="RD23601ST-8B">8b</A> Hardinger SA. Fuchs PL. J. Org. Chem. 1987, 52: 2739

<A NAME="RD23601ST-8C">8c</A> Padwa A. Murphree SS. Ni Z. Watterson SH. J. Org. Chem. 1996, 61: 3829

<A NAME="RD23601ST-8D">8d</A> Cuvigny T. Herve du Penhoat C. Julia M. Tetrahedron 1986, 42: 5321

<A NAME="RD23601ST-8E">8e</A> Backvall J.-E. Ericsson AM. Juntunen S. Nájera C. Yus M. J. Org. Chem. 1993, 58: 5221

<A NAME="RD23601ST-9">9</A> Kociénski PJ. Protecting Groups Thieme Verlag; Stuttgart/New York: 1994.

Experimental Details for the Transformation of 7: LDA was generated by the addition of n-butyllithium 1.6 M (0.25 mL, 0.38 mmol) to a solution of diisopropylamine (54 µL, 0.38 mmol) in THF (1.0 mL) at -78 ºC. After 5 minutes, the mixture was allowed to warm to room temperature, and then recooled to -78 ºC. Compound 7 (80 mg, 0.18 mmol) was then added to the reaction flask via cannula as a solution in THF (1 mL). The reaction mixture was left to stir for one hour at -78 ºC under argon before the addition of saturated ammonium chloride solution (1 mL). The product was extracted into ethyl acetate three times. The organic extracts were combined, washed with water and saturated brine, then dried over anhydrous sodium sulfate, filtered and removed the solvent in vacuo. The mixture was purified by flash silica column chromatography (hexane-ethyl acetate, 9:1) isolating 53 mg, 94% of a mixture 7:3 of cyclopropanes 8 and 9. Selected data for compound 8: [α]²⁰ _D = +17.2º, (c = 0.79, CHCl₃), ¹H NMR (200 MHz, CDCl₃) δ 0.93 (1 H, m, H_β-3), 1.04 (1 H, q, J = 6.4 Hz, H_α-3), 1.24 (1 H, m, H-2), 1.38-1.90 (6 H, m, H-2’, H-3’, H-4’), 3.57 (1 H, m, H_A-5’), 3.71 (1 H, m, H-1), 3.86 (1 H, m, H_B-5’), 4.68 (1 H, m, H-1’), 6.22 and 6.30 (1 H, d, J = 15 Hz, CH=CH-SO₂Ph), 6.54 (1 H, dd, J = 15.0 and 10.0 Hz, CH=CH-SO₂Ph), 7.56 (3 H, m, -SO₂Ph), 7.86 (2 H, m, -SO₂Ph). ¹³C NMR (50 MHz, CDCl₃) δ 16.0 and 17.1 (C-3), 19.3 and 19.4 (C-3’), 21.5 and 22.2 (C-2), 25.5 (C-4’), 29.9 and 30.6 (C-2’), 59.0 (C-1), 62.6 and 62.8 (C-5’), 99.1 (C-1’), 127.5 and 128.2 (CH=CH-SO₂Ph), 127.7 (C_orto, -SO₂Ph), 129.5 (C_meta, -SO₂Ph), 133.4 (C_para, -SO₂Ph), 141.1 (C_ipso, -SO₂Ph), 147.9 and 148.0 (CH=CH-SO₂Ph). EIMS m/z (rel. int.): 309 (M⁺ + 1, 3), 279(5), 195(5), 167(10), 125,(10), 85(100). HRMS C₁₆H₂₀O₄S requires 308,1082, found, 308,1082. IR (liquid film, cm^-1): 3063, 2942, 1620, 1447, 1308, 1146, 1086. Selected data for compound 9: [α]²⁰ _D = -41.7º, (c = 0.87, CHCl₃), ¹H NMR (200 MHz, CDCl₃) δ 0.91 (2 H, m, H-3), 1.08-1.89 (7 H, m, H-2’, H-3’, H-4’, H-2), 3.57 (1 H, m, H_A-5’), 3.76-4.02 (2 H, m, H_B-5’, H-1), 4.42 and 4.75 (1 H, m, H-1’), 6.42 (1 H, m, CH -SO₂Ph), 6.80 (1 H, m, CH=CH -SO₂Ph), 7.56 (3 H, m, -SO₂Ph), 7.88 (2 H, m, -SO₂Ph), ¹³C NMR (50 MHz, CDCl₃) δ 15.8 and 17.0 (C-3), 19.3 and 19.5 (C-3’), 20.5 and 21.1 (C-2), 25.6 (C-4’), 30.3 and 30.6
(C-2’), 57.0 (C-1), 62.6 and 62.8 (C-5’), 99.3 (C-1’) 127.7 (C_orto, -SO₂Ph), 128.6 (CH -SO₂Ph), 129.3 (C_meta, -SO₂Ph), 133.2 (C_para, -SO₂Ph), 141.4 (C_ipso, -SO₂Ph), 146.8 and 147.4 (CH=CH -SO₂Ph). EIMS m/z (rel. int.): 308 (M⁺, 3), 224(5), 195(8), 125(15), 85(100). HRMS C₁₆H₂₀O₄S requires 308,1082, found 308,1092. IR (film, cm^-1): 2945, 1618, 1447, 1317, 1144.

<A NAME="RD23601ST-11">11</A> Militzer H.-C. Schömenauer S. Otte C. Puls C. Hain J. Bräse S. de Meijere A. Synthesis 1993, 998 ; and references cited therein

<A NAME="RD23601ST-12A">12a</A> For general review see: Wong HNC. Hon M.-Y. Tse C.-W. Yip Y.-C. Tanko J. Hudlicky T. Chem. Rev. 1989, 89: 165

<A NAME="RD23601ST-12B">12b</A> Park S.-B. Cha JK. Org. Lett. 2000, 2: 147 ; and references cited therein

Selected data for compound 13: [α]²⁰ _D =-17.2º, (c = 0.40, CHCl₃), ¹H NMR (400 MHz, CDCl₃) δ 0.37 (1 H, q, J = 6.0 Hz, H_α-3), 0.76 (1 H, ddd, J = 9.2, 5.6 and 2.8 Hz, H_β-3), 0.95 (1 H, m, H-2), 1.56-1.73 (3 H, m, CH₂-CH₂ -SO₂Ph, -OH), 3.18 (2 H, m, -CH₂ -SO₂Ph), 3.25 (1 H, dt, J = 6.0, 2.8, 2.8 Hz, H-1), 7.58 (2 H, m, -SO₂Ph), 7.65 (1 H, m, -SO₂Ph), 7.91 (2 H, m, -SO₂Ph), ¹³C NMR (50 MHz, CDCl₃) δ 14.9 (C-3), 19.6 (C-2), 25.2 (CH₂-CH₂ -SO₂Ph), 52.8 (C-1), 56.0 (CH₂ -SO₂Ph), 128.2 (C_orto, -SO₂Ph), 129.5 (C_meta, -SO₂Ph), 133.9 (C_para, -SO₂Ph), 139.5 (C_ipso, -SO₂Ph). EIMS m/z (rel. int.): 226 (M⁺, 5), 184(10), 143(65), 125(30), 84(85), 77(100). HRMS C₁₁H₁₄O₃S requires 226.0664, found 226.0669. IR (liquid film, cm^-1): 3200-3600, 2926, 1447, 1304, 1142, 1086, 689. Selected data for compound 14: [α]²⁰ _D = -8.5º, (c = 0.46, CHCl₃), ¹H NMR (400 MHz, CDCl₃) δ 0.21 (1 H, m, H_α-3), 0.72 (1 H, m, H_β-3), 1.20 (1 H, m, H-2), 1.90 (2 H, m, CH₂-CH₂ -SO₂Ph), 3.25 (2 H, m, CH₂ -SO₂Ph), 3.53 (1 H, dt, J = 6.4, 6.4 and 3.2 Hz, H-1), 7.63 (3 H, m, -SO₂Ph), 7.92 (2 H, m, -SO₂Ph). ¹³C NMR (100 MHz, CDCl₃) δ 13.0 (C-3), 16.5 (C-2), 20.4 (CH₂-CH₂ -SO₂Ph), 49.6 (C-1), 56.4 (CH₂ -SO₂Ph), 127.9 (C_orto, -SO₂Ph), 129.2 (C_meta, -SO₂Ph), 133.6 (C_para, -SO₂Ph), 139.7 (C_ipso, -SO₂Ph). EIMS m/z (rel. int.): 226 (M⁺, 13), 184(12), 143(70), 125(30), 77(100). HRMS C₁₁H₁₄O₃S requires 226.0664, found 226.0684. IR (liquid film, cm^-1): 3200-3600, 3063, 2926, 2855, 1447, 1304, 1144, 1086.