A Synthesis of α-Lithiated Enol Ethers from α-Arenesulfinyl Enol Ethers: Ni(0)- and Pd(0)-Catalysed Coupling of Enol Triflates and Phosphates Derived from Lactones with Sodium Arenethiolates Gives α-Arenesulfanyl Enol Ethers

Abstract

A three-step synthesis of stable and storable α-benzenesulfinyl enol ethers from lactones entails (a) conversion of a lactone to an enol triflate or phosphate; (b) Ni(0) and Pd(0) cross-coupling of the enol triflate or phosphate with a sodium arenethiolate to give an α-arenethio enol ether; and (c) oxidation of an arenethio group to a sulfoxide. The α-benzenesulfinyl enol ethers undergo sulfoxide-lithium exchange on reaction with n-BuLi to give α-lithiated enol ethers thus making the α-benzenesulfinyl group a surrogate for the trialkylstannyl group which has hitherto served as the most common precursor to α-lithiated enol ethers.

Key words

coupling - nickel - palladium - catalysis - sulfoxides - enol ether

References

• 1 Paul R. Tchelitcheff S. C. R. Acad. Sci.  1951,  232:  2230 
• 2 Schöllkopf U. Hänssle P. Liebigs Ann. Chem.  1972,  763:  208 
• 3 Baldwin JE. Höfle GA. Lever OW. J. Am. Chem. Soc.  1974,  96:  7125 
• 4 Friesen RW. J. Chem. Soc., Perkin Trans. 1  2001,  1969 
• 5 Boeckman RK. Bruza KJ. Tetrahedron Lett.  1977,  4187 
• 6 Boeckman RK. Bruza KJ. Tetrahedron  1981,  37:  3997 
• 7 Crich D. Ritchie TJ. Tetrahedron  1988,  44:  2319 
• 8 Paquette LA. Oplinger JA. Tetrahedron  1989,  45:  107 
• 9 Friesen RW. Sturino CF. Daljeet AK. Kolaczewska A. J. Org. Chem.  1991,  56:  1944 
• 10 Nicolaou KC. Hwang C.-K. Duggan ME. J.Chem. Soc., Chem. Commun.  1986,  925 
• 11 Hanessian S. Martin M. Desai RC. J. Chem. Soc., Chem. Commun.  1986,  926 
• 12 Santiago B. Soderquist J. J. Org. Chem.  1992,  57:  5844 
• 13 Barber C. Jarowicki K. Kocienski PJ. Synlett  1991,  197 
• 14 Nicolaou KC. Shi GQ. Gunzner JL. Gaertner P. Yang Z. J. Am. Chem. Soc.  1997,  119:  5467 
• 15 Nicolaou KC. McGarry DG. Sommers PK. J. Am. Chem. Soc.  1990,  112:  3696 
• 16 Lesimple P. Beau JM. Jaurand G. Sinay P. Tetrahedron Lett.  1986,  27:  6201 
• 17 Gunn A. Jarowicki K. Kocienski PJ. Lockhart S. Synthesis  2001,  331 
• 18 McDonald FE. Chem.-Eur. J.  1999,  5:  3103 
• 19 Wildman T. Kocienski PJ. Narquizian R. Whittingham WG. Synthesis  2002,  393 
• 20 Yu W. Jin Z. J. Am. Chem. Soc.  2000,  122:  9840 
• 21 Yu W. Jin Z. J. Am. Chem. Soc.  2001,  123:  3369 
• 22 Milne JE. Jarowicki K. Kocienski PJ. Synlett  2002,  607 
• 23 Milne JE. Jarowicki K. Kocienski PJ. Alonso J. Chem. Commun.  2002,  426 
• 24 Luker T. Hiemstra H. Speckamp WN. J. Org. Chem.  1997,  62:  3592 
• 25 Percec V. Bae J.-Y. Hill DH. J. Org. Chem.  1995,  60:  6895 
• 26 Lockard JP. Schroeck CW. Johnson CR. Synthesis  1973,  485 
• 27 Durst T. LeBelle MJ. Van den Elzen R. Tin K.-C. Can. J. Chem.  1974,  52:  761 
• 28 Neef G. Eder U. Seeger A. Tetrahedron Lett.  1980,  21:  903 
• 29 For alternative mechanisms to sulfoxide-lithium exchange reactions see: Theobald PG. Okamura WH. J. Org. Chem.  1990,  55:  741 
• 30 Zheng N. McWilliams JC. Fleitz FJ. Armstrong JD. Volante RP. J. Org. Chem.  1998,  63:  9606 
• 31 For references to transition metal mediated cross-coupling reactions leading to C-S formation, see: Li GY. Zheng G. Noonan AF. J. Org. Chem.  2001,  66:  8677 
• 32 Sulfoxide-lithium exchange processes have recently been used to prepare glycosyllithiums: Carpintero M. Nieto I. Fernández-Mayoralas A. J. Org. Chem.  2001,  66:  1768 
• 33 It is likely that a previous report of the conversion of anomeric glycosyl sulfoxides to pyranoid glycals using organolithiums involved a sulfoxide-lithium exchange: Casillas M. Gómez AM. López JC. Valverde S. Synlett  1996,  628 
• 34 For the generation of α-halo carbanions from aryl α-haloalkyl sulfoxides and aryl α-haloalkenyl sulfoxides by sulfoxide-metal exchange, see: Satoh T. Takano K. Tetrahedron  1996,  52:  2349 
• 35 Lipton MF. Sorenson CM. Sadler AC. Shapiro RH. J. Organometal. Chem.  1980,  186:  155 
• 36 Aquino M. Cardani S. Fronza G. Fuganti C. Fernandez RP. Tagliani A. Tetrahedron  1991,  47:  7887 
• 37 Carroll FI. Mitchell GN. Blackwell JT. Sobti A. Meck R. J. Org. Chem.  1974,  39:  3890 
• 38 Yato M. Homma K. Ishida A. Tetrahedron  2001,  57:  5353 
• 39 Nicolle JP. Hamon JP. Wakselman M. Bull. Soc. Chim. Fr.  1977,  83 
• 40 Harris L. Jarowicki K. Kocienski PJ. Synlett  1996,  903 
• 41 Meyer WL. Taylor PW. Reed SA. Leister MC. Schneider HJ. Schmidt G. Evans FE. Levine RA. J. Org. Chem.  1992,  57:  291 
• 42 Murahashi S.-i. Naota T. Ito K. Maeda Y. Taki H. J. Org. Chem.  1987,  52:  4319