Palladium-Catalyzed R(sp³)-Zn/R(sp)-SnBu₃ Oxidative Cross-Coupling

Abstract

A novel bond formation through oxidative cross-coupling with desyl chloride as the oxidant has been investigated. The coupling can be carried out under mild conditions. The Csp³-center carbon was involved even in the presence of a β-H, and up to 90% of the desired cross-coupling product was obtained with the secondary Csp³-center substrate.

Key words

oxidative cross-coupling - transmetalation - organotin reagents - organozinc reagents - palladium

References

• 1 Crabtree RH. The Organometallic Chemistry of the Transition Metals   3rd ed.:  Wiley; New York: 2001. 
• 2 Negishi E.-i. de Meijere A. Handbook of Organopalladium Chemistry for Organic Synthesis   Wiley-Interscience; New York: 2002. 
• 3 Tsuji J. Transition Metal Reagents and Catalysts: Innovations in Organic Synthesis   Wiley; Chichester: 2000. 
• 4 de Meijere A. Diederich F. Metal-Catalyzed Cross-Coupling Reactions   2nd ed.:  Wiley-VCH; Weinheim: 2004. 
• 5 Tamao K. Kiso Y. Sumitani K. Kumada M. J. Am. Chem. Soc.  1972,  94:  9268 
• 6 Tamao K. Sumitani K. Kumada M. J. Am. Chem. Soc.  1972,  94:  4374 
• 7 Negishi E. Okukado N. King AO. Van Horn DE. Spiegel BI. J. Am. Chem. Soc.  1978,  100:  2254 
• 8 King AO. Okukado N. Negishi E. J. Chem. Soc., Chem. Commun.  1977,  683 
• 9 Miyaura N. Suzuki A. J. Chem. Soc., Chem. Commun.  1979,  866 
• 10 Stille JK. Pure Appl. Chem.  1985,  57:  1771 
• 11 Kataoka N. Shelby Q. Stambuli JP. Hartwig JF. J. Org. Chem.  2002,  67:  5553 
• 12 Old DW. Wolfe JP. Buchwald SL. J. Am. Chem. Soc.  1998,  120:  9722 
• 13 Cardenas DJ. Angew. Chem. Int. Ed.  2003,  42:  384 
• 14 Altenhoff G. Goddard R. Lehmann CW. Glorius F. Angew. Chem. Int. Ed.  2003,  42:  3690 
• 15 Navarro O. Kelly RA. Nolan SP. J. Am. Chem. Soc.  2003,  125:  16194 
• 16 Eckhardt M. Fu GC. J. Am. Chem. Soc.  2003,  125:  13642 
• 17 Milne JE. Buchwald SL. J. Am. Chem. Soc.  2004,  126:  13028 
• 18 Hamann BC. Hartwig JF. J. Am. Chem. Soc.  1998,  120:  7369 
• 19 Littke AF. Fu GC. J. Org. Chem.  1999,  64:  10 
• 20 Littke AF. Fu GC. Angew. Chem. Int. Ed.  1999,  38:  2411 
• 21 Dai C. Fu GC. J. Am. Chem. Soc.  2001,  123:  2719 
• 22 Hadei N. Kantchev EAB. O’Brien CJ. Organ MG. Org. Lett.  2005,  7:  3805 
• 23 Hadei N. Kantchev EAB. O’Brien CJ. Organ MG. J. Org. Chem.  2005,  70:  8503 
• 24 Campos KR. Klapars A. Waldman JH. Dormer PG. Chen C.-y. J. Am. Chem. Soc.  2006,  128:  3538 
• 25 Barrios-Landeros F. Hartwig JF. J. Am. Chem. Soc.  2005,  127:  6944 
• 26 Hills ID. Netherton MR. Fu GC. Angew. Chem. Int. Ed.  2003,  42:  5749 
• 27 Littke AF. Fu GC. Angew. Chem. Int. Ed.  1999,  37:  3387 
• 28 Collman JP. Hegedus LS. Principles and Applications of Organotransition Metal Chemistry, 2nd ed.   University Science Books; Mill Valley, CA: 1987. 
• 29 Luh T.-Y. Leung M.-k. Wong K.-T. Chem. Rev.  2000,  100:  3187 
• 30 Cardenas DJ. Angew. Chem. Int. Ed.  1999,  38:  3018 
• 31 Culkin DA. Hartwig JF. Organometallics  2004,  23:  3398 
• 32 Casares JA. Espinet P. Fuentes B. Salas G. J. Am. Chem. Soc.  2007,  129:  3508 
• 33 Devasagayaraj A. Stuedemann T. Knochel P. Angew. Chem., Int. Ed. Engl.  1996,  34:  2723 
• 34 Jensen AE. Knochel P. J. Org. Chem.  2002,  67:  79 
• 35 Giovannini R. Stuedemann T. Devasagayaraj A. Dussin G. Knochel P. J. Org. Chem.  1999,  64:  3544 
• 36 Giovannini R. Knochel P. J. Am. Chem. Soc.  1998,  120:  11186 
• 37 Giovannini R. Studemann T. Dussin G. Knochel P. Angew. Chem. Int. Ed.  1998,  37:  2387 
• 38 Zhao Y. Wang H. Hou X. Hu Y. Lei A. Zhang H. Zhu L. J. Am. Chem. Soc.  2006,  128:  15048 
• 39 Lei A. Srivastava M. Zhang X. J. Org. Chem.  2002,  67:  1969 
• 40 Lei A. Zhang X. Org. Lett.  2002,  4:  2285 
• 41 Lei A. Zhang X. Tetrahedron Lett.  2002,  43:  2525 
• 42 Moloney MG. Pinhey JT. Roche EG. J. Chem. Soc., Perkin Trans. 1  1989,  333 
• 43 Djakovitch L. Wagner M. Hartung CG. Beller M. Koehler K. J. Mol. Catal. A: Chem.  2004,  219:  121 
• 44 Knochel P. Jones P. Organozinc Reagents: A Practical Approach   Oxford University Press; Oxford: 1999. 

45

The desired cross-coupling product was mixed with 1,2-diphenylethanone, which was formed from the Zn-enolate IV. Efforts to completely separate the two compounds were unsuccessful.