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

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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

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References

1a Donaldson WA. Tetrahedron 2001, 57: 8589 ; and references cited therein

1b Esposito A. Taddei M. J. Org. Chem. 2000, 65: 9245

For leading references, see:

2a Salaün J. Rappoport Z. In The Chemistry of the Cyclopropyl Group, Rearrangements Involving the Cyclopropyl Group Wiley; New York: 1987. p.809

2b Houben-Weyl: Methods of Organic Chemistry, Carbocyclic Three and Four-membered Ring Systems Vol. E.17: de Meijere A. Thieme Verlag; Stuttgart: 1997.

2c Sylvestre I. Olivier J. Salaün J. Tetrahedron Lett. 2001, 42: 4991 ; and references cited therein

2d Shaffer CL. Morton MD. Hanzlik RP. J. Am. Chem. Soc. 2001, 123: 8502

2e 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:

3a Pietruszka J. Widenmeyer M. Synlett 1997, 977

3b Fontani P. Carboni B. Vaultier M. Maas G. Synthesis 1991, 605

3c Imai T. Mineta H. Nishida S. J. Org. Chem. 1990, 55: 4986

3d Pietruszka J. Witt A. J. Chem. Soc. Perkin Trans. 1 2000, 4293

3e Luithle JEA. Pietruszka J. Witt A. J. Chem. Soc., Chem. Commun. 1998, 2651

3f Taylor RE. Schmidt MJ. Yuan H. Org. Lett. 2000, 2: 601 ; and references cited therein

3g Baird MS. Huber AM. Clegg W. Tetrahedron 2001, 57: 9849

4 McGaffin G. Grimm B. Heinecke U. Michaelsen H. de Meijere A. Walsh R. Eur. J. Org. Chem. 2001, 3559 ; and references cited therein

5a Morikawa T. Saski H. Hanai R. Shibuya A. Taguchi T. Muray E. J. Org. Chem. 1994, 59: 97

5b Evans DA. Burch JD. Org. Lett. 2001, 3: 503

5c Alvarez-Larena A. Piniella JF. Branchadell V. Ortuño RM. J. Org. Chem. 2000, 65: 388

5d Ma D. Cao Y. Yang Y. Cheng D. Org. Lett. 1999, 1: 285

6a Urones JG. Marcos IS. Garrido NM. Basabe P. Bastida AJ. San Feliciano SG. Díez Martín D. Goodman JM. Synlett 1998, 1361

6b Díez Martín D. San Feliciano SG. Marcos IS. Basabe P. Garrido NM. Urones JG. Synthesis 2001, 1069

7a Urones JG. Díez Martín D. Marcos IS. Garrido NM. Basabe P. San Feliciano SG. Coca R. Synlett 1998, 41: 1364

7b Díez Martín D. Templo Beneitez M. Marcos IS. Garrido NM. Basabe P. Urones JG. Synlett 2001, 655

8a Carreño MC. Cid MB. Carcia Ruano JL. Santos M. Tetrahedron Lett. 1998, 39: 1405

8b Hardinger SA. Fuchs PL. J. Org. Chem. 1987, 52: 2739

8c Padwa A. Murphree SS. Ni Z. Watterson SH. J. Org. Chem. 1996, 61: 3829

8d Cuvigny T. Herve du Penhoat C. Julia M. Tetrahedron 1986, 42: 5321

8e Backvall J.-E. Ericsson AM. Juntunen S. Nájera C. Yus M. J. Org. Chem. 1993, 58: 5221

9 Kociénski PJ. Protecting Groups Thieme Verlag; Stuttgart/New York: 1994.

10

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.

11 Militzer H.-C. Schömenauer S. Otte C. Puls C. Hain J. Bräse S. de Meijere A. Synthesis 1993, 998 ; and references cited therein

12a For general review see: Wong HNC. Hon M.-Y. Tse C.-W. Yip Y.-C. Tanko J. Hudlicky T. Chem. Rev. 1989, 89: 165

12b Park S.-B. Cha JK. Org. Lett. 2000, 2: 147 ; and references cited therein

13

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.