Aza-Mannich Condensation of Sulfinimine Promoted by Tetrabutyl­ammonium Fluoride: Synthesis of α,β-Unsaturated Sulfinimine

Xiaoxia Bian; Dan Zhang; Zhiyan Huang; Yong Qin

doi:10.1055/s-2006-956466

Subscribe to RSS

Please copy the URL and add it into your RSS Feed Reader.

https://www.thieme-connect.de/rss/thieme/en/10.1055-s-00000083.xml

Share / Bookmark

Facebook Linkedin Weibo

Download PDF

Synlett 2006(20): 3419-3422
DOI: 10.1055/s-2006-956466

LETTER

Aza-Mannich Condensation of Sulfinimine Promoted by Tetrabutylammonium Fluoride: Synthesis of α,β-Unsaturated Sulfinimine

Xiaoxia Bian, Dan Zhang, Zhiyan Huang, Yong Qin*
Department of Chemistry of Medicinal Natural Products and Key Laboratory of Drug Targeting, West China School of Pharmacy and State Key Laboratory of Biotherapy, Sichuan University, Chengdu 610041, P. R. of China
e-Mail: yongqin@scu.edu.cn;

Further Information

Publication History

Received 12 July 2006
Publication Date:
08 December 2006 (online)

Abstract
Full Text
References

Permissions and Reprints All articles of this category

Abstract

Self-condensation of tert-butanesulfinimine 5 was realized in the presence of tetrabutylammonium fluoride to afford α,β-unsaturated sulfinimine 8 in moderate to high yields with high geometric selectivities. The synthesized α,β-unsaturated sulfinimine 8 was demonstrated to be a versatile intermediate for the syntheses of enal 4 and chiral allyl amine 11.

Key words

tert-butanesulfinimine - self-condensation - tetrabutylammonium fluoride - enal - chiral allyl amine

References and Notes

1 Stork G. Brizzolara A. Landesman H. Szmuszkovicz J. Terrell R. J. Am. Chem. Soc. 1963, 85: 207

Crossref Search in Google Scholar
For reviews on sulfinimine chemistry, see:
2a Zhou P. Chen B.-C. Davis FA. Tetrahedron 2004, 60: 8003

Crossref Search in Google Scholar
2b Ellman JA. Owens TD. Pure Appl. Chem. 2003, 75: 39

Crossref Search in Google Scholar
2c Ellman JA. Owens TD. Tang TP. Acc. Chem. Res. 2002, 35: 984

Crossref Search in Google Scholar
2d Davis FA. Zhou P. Chen B.-C. Chem. Soc. Rev. 1998, 27: 13

Crossref Search in Google Scholar
3a Jiang W.-L. Chen C. Marinkovic D. Tran JA. Chen CW. Arellano LM. White NS. Tucci F. J. Org. Chem. 2005, 70: 8924

Crossref Search in Google Scholar
3b Mukade T. Dragoli DR. Ellman J. J. Comb. Chem. 2003, 5: 590

Crossref Search in Google Scholar
3c Kells KW. Chong JM. Org. Lett. 2003, 5: 4215

Crossref Search in Google Scholar
3d Tang TP. Volkman SK. Ellman JA. J. Org. Chem. 2001, 66: 8772

Crossref Search in Google Scholar
3e Davis FA. McCoull W. J. Org. Chem. 1999, 64: 3396

Crossref Search in Google Scholar
3f Cogan DA. Ellman JA. J. Am. Chem. Soc. 1999, 121: 268

Crossref Search in Google Scholar
3g Cogan DA. Liu G.-C. Ellman J. Tetrahedron 1999, 55: 8883

Crossref Search in Google Scholar
4a Davis FA. Deng J. Org. Lett. 2004, 6: 2789

Crossref PubMed Search in Google Scholar
4b Davis FA. Prasad KR. Nolt MB. Wu Y. Org. Lett. 2003, 5: 925

Crossref PubMed Search in Google Scholar
4c Jacobsen MF. Skrydstrup T. J. Org. Chem. 2003, 68: 7112

Crossref PubMed Search in Google Scholar
4d Tang T. Ellman JA. J. Org. Chem. 2003, 67: 12

Crossref PubMed Search in Google Scholar
4e Tang T. Ellman JA. J. Org. Chem. 1999, 64: 12

Crossref PubMed Search in Google Scholar
5a Lanter JC. Chen H.-F. Zhang X.-Q. Sui Z.-H. Org. Lett. 2005, 7: 5905

Crossref PubMed Search in Google Scholar
5b Kochi T. Tang TP. Ellman JA. J. Am. Chem. Soc. 2002, 124: 6518

Crossref PubMed Search in Google Scholar
6a Xiao X. Wang H.-W. Huang Z.-Y. Yang J. Bian X.-X. Qin Y. Org. Lett. 2006, 8: 139

Thieme Connect Search in Google Scholar
6b Wang Y. He Q.-F. Wang H.-W. Zhou X. Huang Z.-Y. Qin Y. J. Org. Chem. 2006, 71: 1588

Thieme Connect Search in Google Scholar
6c Huang Z.-Y. Zhang M. Wang Y. Qin Y. Synlett 2005, 1334

Thieme Connect
7 The α,β-unsaturated sulfinimine 8 was also prepared by Ti(Oi-Pr)₄-catalyzed condensation of enal with tert-butanesulfinamide 9. See: McMahon JP. Ellman JA. Org. Lett. 2005, 7: 5393

Crossref Search in Google Scholar
As a class of important plant and insect metabolites with antimicrobial properties, there are several examples describing preparation of enals. See:
8a Kiyooka S. Fujimoto H. Mishima M. Kobayashi S. Uddin K. Fujio M. Tetrahedron Lett. 2003, 44: 927

Crossref Search in Google Scholar
8b Shimizu K. Hayashi E. Inokuchi T. Kodama T. Hagiwara H. Kitayama Y. Tetrahedron Lett. 2002, 43: 9073

Crossref Search in Google Scholar
8c Engman L. Vasil’ev A. J. Org. Chem. 2000, 65: 2151

Crossref Search in Google Scholar
8d Hagiwara H. Ono H. Komatsubara N. Hoshi T. Suzuki T. Ando M. Tetrahedron Lett. 1999, 40: 6627

Crossref Search in Google Scholar
8e Suyama K. Arakawa T. Adachi S. J. Agric. Food Chem. 1981, 29: 875

Crossref Search in Google Scholar

9

Representative Procedure of Self-Condensation: To a solution of 5 (1 mmol) in anhyd Et₂O (10 mL) was added anhyd TBAF (1.2 mmol, dried by P₂O₅ in vacuum condition). The biphasic mixture was stirred at r.t. for 30 min and then diluted with Et₂O (30 mL). After washing of the mixture with sat. NaCl solution, the solvent was evaporated to give a residue. The residue was either subjected to chromatography to give α,β-unsaturated sulfinimine 8 and tert-butanesulfinamide 9, or was subjected to hydrolysis to give enal 4.
Data for 8a (major isomer): ¹H NMR (400 MHz, CDCl₃): δ = 0.85-0.91 (m, 6 H), 1.21 (s, 9 H), 1.23-1.50 (m, 18 H), 2.28 (q, J = 6.4 Hz, 2 H), 2.31-2.46 (m, 2 H), 6.20 (t, J = 7.6 Hz, 1 H), 8.05 (s, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 14.0, 22.4, 22.5, 22.6, 25.8, 28.7, 28.8, 28.9, 29.0, 29.3, 29.4, 29.7, 31.6, 31.7, 57.1, 139.5, 148.8, 166.3. HRMS: m/z [M + H⁺] calcd for C₂₀H₄₀NOS: 342.2825; found: 342.2813.
Data for 8b (major isomer): ¹H NMR (400 MHz, CDCl₃): δ = 0.95 (t, J = 7.2 Hz, 3 H), 1.01 (t, J = 7.6 Hz, 3 H), 1.20 (s, 9 H), 1.47 (q, J = 7.2 Hz, 2 H), 2.27 (q, J = 7.6 Hz, 2 H), 2.32-2.48 (m, 2 H), 6.18 (t, J = 7.6 Hz, 1 H), 8.04 (s, 1 H). ¹³C NMR (50 MHz, CDCl₃): δ = 13.5, 13.7, 19.1, 22.5, 29.7, 30.6, 57.1, 141.0, 148.1, 166.0. HRMS: m/z [M + Na⁺] calcd for C₁₂H₂₃NNaOS: 252.1393; found: 252.1397.
Data for (S)-8c: [a]²⁰ _D +131.9 (c = 1.0, CHC1₃). ¹H NMR (400 MHz, CDCl₃): δ = 0.98 (s, 9 H), 2.68-2.81 (m, 4 H), 3.72 (dd, J ₁ = 27.6 Hz, J ₂ = 14.8 Hz, 2 H), 6.45 (t, J = 6.8 Hz, 1 H), 7.05-7.31 (m, 10 H), 8.10 (s, 1 H). ¹³C NMR (100 MHz, CDCl): δ = 22.2, 31.0, 31.6, 34.8, 57.1, 125.9, 126.2, 128.1, 128.2, 128.4, 128.5, 138.3, 139.3, 140.6, 148.2, 165.4. HRMS: m/z [M + Na⁺] calcd for C₂₂H₂₇NNaOS: 376.1706; found: 376.1704.
Data for 8d (major isomer): ¹H NMR (400 MHz, CDCl₃): δ = 1.20 (s, 9 H), 1.78-1.87 (m, 2 H), 2.03 (s, 3 H), 2.07 (s, 3 H), 2.40-2.46 (m, 2 H), 2.70-2.80 (m, 2 H), 4.05-4.18 (m, 4 H), 6.34 (t, J = 7.6 Hz, 1 H), 8.10 (s, 1 H). ¹³C NMR (50 MHz, CDCl₃): δ = 20.9, 22.5, 24.2, 25.5, 27.9, 29.7, 57.3, 62.6, 63.6, 135.5, 149.1, 165.5, 170.7, 171.1. HRMS: m/z [M + H⁺] calcd for C₁₆H₂₈NO₅S: 346.1682; found: 346.1685.
Data for 8e (major isomer): ¹H NMR (400 MHz, CDCl₃): δ = 1.15 (s, 9 H), 1.72-1.82 (m, 2 H), 2.42-2.50 (m, 2 H), 2.70-2.84 (m, 2 H), 3.44-3.54 (m, 4 H), 4.47 (s, 2 H), 4.48 (s, 2 H), 6.30 (t, J = 7.6 Hz, 1 H), 7.24-7.38 (m, 10 H), 8.06 (s, 1 H). ¹³C NMR (50 MHz, CDCl₃): δ = 22.4, 25.8, 26.5, 26.7, 57.0, 68.4, 69.2, 72.5, 72.6, 127.4, 127.5, 126.2, 126.3, 135.7, 138.3, 149.8, 165.7. HRMS: m/z [M + H⁺] calcd for C₂₆H₃₆NOS: 442.2410; found: 442.2422.
Data for 4g (major isomer): ¹H NMR (400 MHz, CDCl₃): δ = 1.55-1.70 (m, 6 H), 2.30-2.42 (m, 4 H), 3.42-3.51 (m, 4 H), 4.48 (s, 2 H), 4.49 (s, 2 H), 6.47 (t, J = 7.6 Hz, 1 H), 7.25-7.36 (m, 10 H), 9.36 (s, 1 H). ¹³C NMR (50 MHz, CDCl₃): δ = 20.7, 25.4, 26.5, 26.6, 26.7, 29.4, 69.7, 69.8, 72.8, 72.9, 127.4, 127.5, 127.6, 128.3, 128.4, 138.4, 138.5, 143.2, 155.3, 195.1. HRMS: m/z [M + Na⁺] calcd for C₂₄H₃₀NaO₃: 389.2087; found: 389.2089.
Data for 4h (major isomer): ¹H NMR (400 MHz, CDCl₃): δ = 1.38-1.57 (m, 6 H), 1.57-1.70 (m, 4 H), 2.25 (t, J = 7.6 Hz, 2 H), 2.34 (q, J = 7.2 Hz, 2 H), 3.42-3.50 (m, 4 H), 4.48 (s, 2 H), 4.50 (s, 2 H), 6.43 (t, J = 7.6 Hz, 1 H), 7.24-7.38 (m, 10 H), 9.35 (s, 1 H). ¹³C NMR (50 MHz, CDCl₃): δ = 23.7, 25.3, 26.0, 28.5, 28.7, 29.5, 29.6, 70.1, 72.8, 76.4, 77.0, 77.7, 127.4, 127.5, 127.6, 128.3, 128.4, 138.3, 138.4, 143.5, 155.3, 195.2. HRMS: m/z [M + Na⁺] calcd for C₂₆H₃₄NaO₃: 417.2400; found: 417.2388.
Data for 10 (Z major isomer): ¹H NMR (400 MHz, CDCl₃): δ = 0.98 (s, 9 H), 4.06 (dd, J ₁ = 19.6 Hz, J ₂ = 15.2 Hz, 2 H), 7.14-7.31 (m, 5 H), 7.41 (s, 1 H), 7.57 (d, J = 8.8 Hz, 2 H), 8.21 (d, J = 9.2 Hz, 2 H), 8.36 (s, 1 H). ¹³C NMR (100 MHz, CDCl₃): δ = 22.3, 32.6, 57.8, 123.9, 126.4, 127.9, 128.7, 129.9, 138.2, 140.3, 141.6, 142.2, 147.6, 165.0. HRMS: m/z [M + Na⁺] calcd for C₂₀H₂₂N₂NaO₃S: 393.1243; found: 393.1235. Data for 10 (E minor isomer): ¹H NMR (400 MHz, CDCl₃): δ = 0.98 (s, 9 H), 4.16 (dd, J ₁ = 24.8 Hz, J ₂ = 16.4 Hz, 2 H), 7.35 (d, J = 8.4 Hz, 2 H), 7.38-7.42 (m, 5 H), 7.46 (s, 1 H), 8.14 (d, J = 8.8 Hz, 2 H), 8.36 (s, 1 H).

10

Representative Procedure of Grignard Addition to 8c: To a solution of 8c (1 mmol) in anhyd CH₂Cl₂ (10 mL) at 0 °C was added Grignard reagent (3 equiv). After being stirred for 1-5 h, the mixture was poured into sat. NH₄Cl solution, and the solution was extracted with CH₂Cl₂. The combined organic phases were dried with Na₂SO₄. After removing the solvent, the residue was subjected to chromatography to give allyl amine 11. The dr was determined by ¹H NMR analysis of crude 11. The absolute configuration of amine in 11 was not determined due to lack of comparable rotation data of structurally similar chiral amine.
Data for 11a (major isomer): [α]²⁰ _D +11.9 (c = 1.0, CHC1₃). ¹H NMR (400 MHz, CDCl₃): δ = 1.14 (s, 9 H), 2.32 (s, 3 H), 2.43-2.50 (m, 2 H), 2.71 (t, J = 7.6 Hz, 2 H), 3.10 (d, J = 15.6 Hz, 1 H), 3.26 (d, J = 4.0 Hz, 1 H), 3.40 (d, J = 15.6 Hz, 1 H), 4.82 (d, J = 4.0 Hz, 1 H), 5.89 (t, J = 7.2 Hz, 1 H), 6.94 (d, J = 6.8 Hz, 2 H), 7.09-7.30 (m, 12 H). ¹³C NMR (50 MHz, CDCl₃): δ = 21.1, 22.6, 30.0, 34.1, 35.7, 55.7, 63.1, 125.7, 125.9, 127.5, 128.3, 128.3, 128.5, 129.2, 129.5, 137.4, 137.8, 138.1, 139.3, 141.6. HRMS: m/z [M + H⁺] calcd for C₂₉H₃₆NOS: 446.2512; found: 446.2521.
Date for 11b (major isomer): [α]²⁰ _D +33.5 (c = 1.0, CHC1₃). ¹H NMR (400 MHz, CDCl₃): δ = 1.15 (s, 9 H), 1.28 (s, 3 H), 2.42-2.48 (m, 2 H), 2.73 (t, J = 7.6 Hz, 2 H), 2.91 (d, J = 5.6 Hz, 1 H), 3.41 (dd, J ₁ = 23.2 Hz, J ₂ = 15.6 Hz, 2 H), 3.88 (m, 1 H), 5.73 (t, J = 7.6 Hz, 1 H), 7.08 (d, J = 7.2 Hz, 2 H), 7.16-7.35 (m, 8 H). ¹³C NMR (50 MHz, CDCl₃): δ = 22.4, 22.6, 30.2, 33.4, 35.7, 55.5, 56.8, 125.9, 126.0, 128.3, 128.4, 128.5, 139.1, 139.7, 141.7. HRMS: m/z [M + H⁺] calcd for C₂₃H₃₂NOS: 370.2199; found: 370.2210.
Date for 11c (major isomer): [α]²⁰ _D +34.0 (c = 1.0, CHC1₃). ¹H NMR (400 MHz, CDCl₃): δ = 0.77 (d, J = 6.8 Hz, 3 H), 0.90 (d, J = 6.8 Hz, 3 H), 1.07 (s, 9 H), 1.70-1.74 (m, 1 H), 2.44-2.50 (m, 2 H), 2.68-2.72 (m, 2 H), 3.12 (d, J = 3.6 Hz, 1 H), 3.31-3.41 (m, 2 H), 3.43-3.44 (m, 1 H), 5.63 (t, J = 7.2 Hz, 1 H), 7.10-7.28 (m, 10 H). ¹³C NMR (100 MHz, CDCl₃): δ = 18.6, 20.0, 22.3, 30.2, 30.9, 33.7, 35.6, 55.2, 67.3, 76.5, 76.8, 77.2, 125.7, 125.8, 128.1, 128.3, 128.5, 130.7, 136.5, 139.4, 141.5. HRMS: m/z [M + Na⁺] calcd for C₂₅H₃₅NNaOS: 420.2332; found: 420.2337.
Date for 11d (major isomer): [α]²⁰ _D +15.3 (c = 1.0, CHC1₃). ¹H NMR (400 MHz, CDCl₃): δ = 0.92 (s, 9 H), 1.07 (s, 9 H), 2.32-2.42 (m, 2 H), 2.65 (t, J = 8.0 Hz, 2 H), 3.24-3.28 (m, 2 H), 3.56-3.60 (m, 2 H), 5.63 (t, J = 7.2 Hz, 1 H), 7.10 (d, J = 6.8 Hz, 2 H), 7.14-7.30 (m, 8 H). ¹³C NMR (100 MHz, CDCl₃): δ = 22.3, 27.2, 29.5, 30.4, 35.4, 36.0, 55.2, 68.1, 125.6, 128.0, 128.1, 128.2, 128.6, 132.4, 139.1, 141.5. HRMS: [M + H⁺] calcd for C₂₆H₃₈NOS: 412.2669; found: 412.2653.