Benzylsulfanyloxazolines in Palladium-Catalyzed Cross-Coupling Reactions: A Novel Approach to Chiral Oxazolines

Abstract

Various 2-benzylsulfanyl-1,3-oxazolines were synthesized and engaged in a copper-promoted palladium-catalyzed cross-coupling reaction with a range of organoboryl and organostannyl reagents to produce 2-aryl- or 2-hetaryl-substituted oxazolines. Protected and unprotected carbohydrate backbones were shown to be compatible with the reaction conditions. This approach opens a new versatile access to chiral oxazoline structures.

Key words

palladium - carbohydrates - cross-coupling - copper - sulfur

References

• For review, see:
• 1a Heck RF. Palladium Reagents in Organic Synthesis   Academic Press; New York: 1985. 
• 1b Tsuji J. Palladium Reagents and Catalysts: Innovations in Organic Synthesis   Wiley & Sons; New York: 1995. 
• 1c Stille JK. Angew. Chem., Int. Ed. Engl.  1986,  25:  508 
• 1d Miyaura N. Suzuki A. Chem. Rev.  1995,  95:  2457 
• 1e Littke AF. Fu GC. Angew. Chem. Int. Ed.  2002,  41:  4176 
• 1f Dubbaka SR. Vogel P. Angew. Chem. Int. Ed.  2005,  44:  7674 
• 2a Malleron J.-L. Fiaud J.-C. Legros J.-Y. Handbook of Palladium-Catalysed Organic Reactions   Academic Press; London: 1997. 
• 2b Srogl J. Allred GD. Liebeskind LS. J. Am. Chem. Soc.  1997,  119:  12376 
• 2c Srogl J. Liu W. Marshall D. Liebeskind LS. J. Am. Chem. Soc.  1999,  121:  9449 
• 2d Darses S. Genêt J.-P. Brayer J.-L. Demoute J.-P. Tetrahedron Lett.  1997,  38:  4393 
• 2e Kikukawa K. Kono K. Wada F. Matsuda T. J. Org. Chem.  1983,  48:  1333 
• 2f Pridgen LN. J. Org. Chem.  1981,  46:  5402 
• 3a Liebeskind LS. Srogl J. J. Am. Chem. Soc.  2000,  122:  11260 
• 3b Savarin C. Srogl J. Liebeskind LS. Org. Lett.  2001,  3:  91 
• 3c Egi M. Liebeskind LS. Org. Lett.  2003,  5:  801 
• 3d Kusturin CL. Liebeskind LS. Neumann WL. Org. Lett.  2002,  4:  983 
• 3e Alphonse F.-A. Suzenet F. Keromnes A. Lebret B. Guillaumet G. Synlett  2002,  447 
• 3f Liebeskind LS. Srogl J. Org. Lett.  2002,  4:  979 
• 3g Alphonse F.-A. Suzenet F. Keromnes A. Lebret B. Guillaumet G. Org. Lett.  2003,  5:  803 
• 3h Richardson C. Rewcastle GW. Hoyer D. Denny WA. J. Org. Chem.  2005,  70:  7436 
• 4 Velazquez F. Olivo HF. Curr. Org. Chem.  2002,  6:  1 
• 5a Nagao Y. Yamada S. Kumagai T. Ochiai M. Fujita E. J. Chem. Soc., Chem. Commun.  1985,  1418 
• 5b Hsiao CN. Liu L. Miller MJ. J. Org. Chem.  1987,  52:  2201 
• 5c Kazmierczak F. Helquist P. J. Org. Chem.  1989,  54:  3988 
• 5d Yan TH. Lee HC. Tan CW. Tetrahedron Lett.  1993,  34:  3559 
• 5e Yan TH. Tan CW. Lee HC. Huang TY. J. Am. Chem. Soc.  1993,  115:  2613 
• 5f Hsiao CN. Liu L. Miller MJ. J. Org. Chem.  1995,  60:  3301 
• 5g Su DW. Wang YC. Yan TH. Tetrahedron Lett.  1999,  40:  4197 
• 5h Crimmins MT. King BW. Tabet EA. Chaudhary K. J. Org. Chem.  2001,  66:  894 
• 5i Guz NR. Phillips A. J. Org. Lett.  2002,  4:  2253 
• 5j Crimmins MT. Katz JD. Washburn DG. Allwein SP. McAtee LF. J. Am. Chem. Soc.  2002,  124:  5661 
• 5k Meyers AI. J. Org. Chem.  2005,  70:  6137 
• 6a Gueyrard D. Grumel V. Leoni O. Palmieri S. Rollin P. Heterocycles  2000,  52:  827 
• 6b Gueyrard D. Leoni O. Palmieri S. Rollin P. Tetrahedron: Asymmetry  2001,  12:  337 
• 6c Girniene J. Gueyrard D. Tatibouët A. Sackus A. Rollin P. Tetrahedron Lett.  2001,  42:  2977 
• 6d Girniene J. Tatibouët A. Sackus A. Yang J. Holman GD. Rollin P. Carbohydr. Res.  2003,  338:  711 
• 6e Girniene J. Apremont G. Tatibouët A. Sackus A. Rollin P. Tetrahedron  2004,  60:  2609 
• 6f Pridgen LN. Killmer LB. J. Org. Chem.  1981,  46:  5402 
• 6g Pridgen LN. Killmer LB. Webb RL. J. Org. Chem.  1982,  47:  1985 
• 6h Chenard BL. J. Org. Chem.  1983,  48:  2610 
• 8a Desimoni G. Faita G. Jorgensen KA. Chem. Rev.  2006,  106:  3561 
• 8b Corey EJ. Imai N. Zhang H.-Y. J. Am. Chem. Soc.  1991,  113:  728 
• 8c Ojima I. Catalytic Asymmetric Synthesis   Wiley-VCH; New York: 2000. 
• 8d Hallman K. Macedo E. Nordström K. Moberg C. Tetrahedron: Asymmetry  1999,  10:  4037 ; and references therein
• 8e Johnson JS. Evans DA. Acc. Chem. Res.  2000,  33:  325 
• 8f Ghosh AK. Mathivanan P. Capiello J. Tetrahedron: Asymmetry  1998,  9:  1 
• 8g Imai Y. Zhang W. Kida T. Nakatsuji Y. Ikeda I. Tetrahedron: Asymmetry  1996,  7:  2453 
• 9 Parlow JJ. Vazquez ML. Flynn DL. Bioorg. Med. Chem. Lett.  1998,  8:  2391 
• 10 Peters D. Hörnfeldt A.-B. Gronowitz S. J. Heterocycl. Chem.  1990,  27:  2165 
• 11 Fülöp F. Csirinyi G. Bernath G. Synthesis  1985,  1149 

7

To our knowledge, only one example of a Pd cross-coupling reaction using an alkylsulfanyl group connected to a non-heteroaryl structure has ever been described. [3d]