Diastereoselective Synthesis of Enantiopure Homopropargylic N-tert-Butylsulfinylamines

Abstract

The diastereoselective synthesis of enantiopure homopropargylic amines by propargylation of various N-tert-butylsulfinylimines (tBS-imines) with 1-trimethylsilyl allenylzinc bromide is presented.

Key words

amines - asymmetric synthesis - chiral auxiliaries - im­ines - zinc

References and Notes

• 1a Acetylene Chemistry, Chemistry, Biology and Material Science   Diederich F. Stang PJ. Tykwinski RR. Wiley-VCH; Weinheim: 2005. 
• 1b Hegedus LS. In Transition Metals in the Synthesis of Complex Organic Molecules   2nd ed.:  University Science Books; Mill Valley (USA): 1999. 
• 1c Parrodi CA. Walsh PJ. Angew. Chem. Int. Ed.  2009,  48:  4679 
• 2 Ding C.-H. Hou X.-L. Chem. Rev.  2011,  111:  1914 
• For recent regioselective propargylation of imines, see:
• 3a Saidi MR. Azizi N. Tetrahedron: Asymmetry  2002,  13:  2523 
• 3b Kagoshima H. Uzawa T. Akiyama T. Chem. Lett.  2002,  298 
• 3c Song Y. Okamoto S. Sato F. Tetrahedron Lett.  2002,  43:  8635 
• 3d Prajapati D. Laskar DD. Gogoi BJ. Devi G. Tetrahedron Lett.  2003,  44:  6755 
• 3e Alcaide B. Almendros P. Aragoncillo C. Rodriguez-Acebes R. Synthesis  2003,  1163 
• 3f Miyabe H. Yamaoka Y. Naito T. Takemoto Y. J. Org. Chem.  2004,  69:  1415 
• 3g Lee PH. Kim H. Lee K. Kim M. Noh K. Kim H. Seomoon D. Angew. Chem. Int. Ed.  2005,  44:  1840 
• 3h Schneider U. Sugiura M. Kobayashi S. Adv. Synth. Catal.  2006,  348:  323 
• 3i Jiang B. Tian H. Tetrahedron Lett.  2007,  48:  7942 
• 3j Yanagisawa A. Suzuki T. Koide T. Okitsu S. Arai T. Chem. Asian J.  2008,  3:  1793 
• 3k Kouznetsov VV. Méndez LYV. Synthesis  2008,  491 
• 3l For recent examples of asymmetric propargylation of imines, see: Fuchibe K. Hatemata R. Akiyama T. Tetrahedron  2006,  62:  11304 
• 3m For allenylboration, see: Gonzalez AZ. Soderquist JA. Org. Lett.  2007,  9:  1081 
• For oxazolidine synthesis of homopropargylic amines, see:
• 3n Guesne S. Comesse S. Kadouri-Puchot C. Lett. Org. Chem.  2006,  3:  315 
• 3o Comesse S. Bertin B. Kadouri-Puchot C. Tetrahedron Lett.  2004,  45:  3807 
• 3p Agami C. Comesse S. Kadouri-Puchot C. J. Org. Chem.  2002,  67:  1496 
• 4 Jiang H. Holub N. Paixão MW. Tiberi C. Falcicchio A. Jørgensen KA. Chem. Eur. J.  2009,  15:  9638 
• For leading references on tBS-imines, see:
• 5a Ellman JA. Owens TD. Tang TP. Acc. Chem. Res.  2002,  356:  984 
• 5b Ellman JA. Pure Appl. Chem.  2003,  75:  39 
• 5c Zhou P. Chen B.-C. Davies FA. Tetrahedron  2004,  60:  8003 
• 5d Senanayake CH. Krishnamurthy D. Lu Z.-H. Han Z. Gallou I. Aldrichimica Acta  2005,  38:  93 
• 5e Morton D. Stockman RA. Tetrahedron  2006,  62:  8869 
• 5f Ferreira F. Botuha C. Chemla C. Perez-Luna A. Chem. Soc. Rev.  2009,  38:  1162 
• 5g Robak MT. Herbage MA. Ellman JA. Chem. Rev.  2010,  110:  3600 
• 6a Chemla F. Ferreira F. J. Org. Chem.  2004,  69:  8244 
• 6b Chemla F. Ferreira F. Synlett  2004,  983 
• 6c Ferreira F. Audouin M. Chemla F. Chem. Eur. J.  2005,  11:  5269 
• 6d Botuha C. Chemla F. Ferreira F. Pérez-Luna A. Roy B. New J. Chem.  2007,  31:  1552 
• 7a Palais L. Chemla F. Ferreira F. Synlett  2006,  1039 
• 7b Chemla F. Ferreira F. Synlett  2006,  2613 
• 7c Chemla F. Ferreira F. Gaucher X. Palais L. Synthesis  2007,  1235 
• 7d Roy B. Pérez-Luna A. Ferreira F. Botuha C. Chemla F. Tetrahedron Lett.  2008,  49:  1534 
• 8 Voituriez A. Pérez-Luna A. Ferreira F. Botuha C. Chemla F. Org. Lett.  2009,  11:  931 
• 9a Voituriez A. Ferreira F. Chemla F. Org. Lett.  2007,  9:  4705 
• 9b Voituriez A. Ferreira F. Chemla F. J. Org. Chem.  2007,  72:  5358 
• 9c Ferreira F. Botuha C. Chemla F. Perez-Luna A. J. Org. Chem.  2009,  74:  2238 
• 9d Séguin C. Ferreira F. Botuha C. Chemla F. Perez-Luna A. J. Org. Chem.  2009,  74:  6986 
• 9e Hélal B. Ferreira F. Botuha C. Chemla F. Pérez-Luna A. Synlett  2009,  3115 
• 9f Louvel J. Botuha C. Chemla F. Demont E. Ferreira F. Pérez-Luna A. Eur. J. Org. Chem.  2010,  2921 
• 9g Botuha C. Chemla F. Ferreira F. Louvel J. Pérez-Luna A. Tetrahedron: Asymmetry  2010,  21:  1147 
• 10 Hashmi ASK. Schäfer S. Bats JW. Frey W. Rominger F. Eur. J. Org. Chem.  2008,  4891 
• 11 Fandrick DR. Johnson CS. Fandrick KR. Reeves JT. Tan Z. Lee H. Song JJ. Yee NK. Senanayake CH. Org. Lett.  2010,  12:  748 
• For the correlation with reported homoallylic amines, see:
• 13a Sun X.-W. Xu M.-H. Lin G.-Q. Org. Lett.  2006,  8:  4979 ; and references cited therein
• 13b Rech JC. Yato M. Duckett D. Ember B. LoGrasso PV. Bergman RG. Ellman JA. J. Am. Chem. Soc.  2007,  129:  490 
• 14 For the correlation with the reported antipode of amino alcohol 6, see: Farmer JJ. Schroeder F. Meinwald J. Helv. Chim. Acta  2000,  83:  2594 
• 15 Denolf B. Mangelinckx S. Tornoos KW. De Kimpe N. Org. Lett.  2006,  8:  3129 
• 16 Tang TP. Volkman SK. Ellman JA. J. Org. Chem.  2001,  66:  8772 
• 17 Evans JW. Ellman JA. J. Org. Chem.  2003,  68:  9948 
• 18 Weix DJ. Ellman JA. Org. Lett.  2003,  5:  1317 
• 19 Barrow JC. Ngo PL. Pellicore JM. Selnick HG. Natermet PG. Tetrahedron Lett.  2001,  42:  2051 

12

Typical procedure for the preparation of 3a-h (Table  [²] ): To a solution of 1-trimethylsilylpropyne (296 µL, 2.00 mmol) in THF (7 mL) was added s-BuLi (1.3 m in pentane, 1.54 mL, 2.00 mmol) at such a rate that the internal temperature did not exceed -45 ˚C. When the addition was complete, the reaction mixture was warmed to -20 ˚C over a period of 20 min. After 45 min of stirring at -20 ˚C, the reaction mixture turned bright yellow and was cooled to -35 ˚C prior to the addition of ZnBr₂ (1 M in THF, 2.00 mL, 2.00 mmol) over a period of 5 min. After 30 min stirring at -35 ˚C, the resulting colorless mixture was cooled to -78 ˚C (for 2a) or warmed to 20 ˚C (for 2b-h). Sulfinylimine 2a-h (1.00 mmol) in THF (1 mL) was then added dropwise. The reaction mixture was stirred at r.t. until the reaction was complete (reaction monitored by TLC; ˜30 min) then quenched by addition of NH₄Cl/NH₃ (2:1), extracted with Et₂O, dried (MgSO₄), and concentrated to give 3a-h, which were purified by flash chromatography over silica gel