Zirconocene-Induced Cocyclisation/Elimination Reactions of 2-Heterosubstituted 1,6-Dienes and 1,6-Enynes

Abstract

Zirconocene-mediated cocyclisation of 2-heterosubstituted-1,6-dienes and -enynes gave zirconacycles bearing an endocyclic β-leaving group which eliminated under the reaction conditions to provide exocyclic alkylidene groups. The scope of this cyclisation/elimination has been investigated along with further elaboration of the monosubstituted zirconocene intermediates by insertion of alkenyl carbenoids.

Key words

zirconium - cyclisation - elimination - alkylidene - carbenoid insertion

References

• 1a Negishi E. Zirconium-Promoted Bicyclization of Enynes, In Comprehensive Organic Synthesis   Vol. 5:  Trost BM. Fleming I. Pergamon; Oxford: 1991.  p.1163 
• 1b Broene RD. Transition Metal Alkyl Complexes: Reductive Dimerization of Alkenes and Alkynes, In Comprehensive Organometallic Chemistry II: A Review of the Literature 1982-1994   Vol. 12:  Abel EW. Stone FGA. Wilkinson G. Pergamon; Oxford: 1995.  p.323-348  
• 2a Millward DB. Waymouth RM. Organometallics  1997,  16:  1153 
• 2b Kotora M. Gao G. Li Z. Xi Z. Takahashi T. Tetrahedron Lett.  2000,  41:  7905 
• 3 Takahashi T. Kondakov DY. Xi Z. Suzuki N. J. Am. Chem. Soc.  1995,  117:  5871 
• 4 Barluenga J. Alvarez-Rodrigo L. Rodriguez F. Fananas FJ. Angew. Chem. Int. Ed.  2004,  43:  3932 
• 5 Barluenga J. Rodriguez F. Alvarez-Rodrigo L. Zapico JM. Fananas FJ. Chem. Eur. J.  2004,  10:  109 
• 6 Chinkov N. Chechik H. Majumdar S. Liard A. Marek I. Synthesis  2002,  2473 
• 7 Nakajima R. Urabe H. Sato F. Chem. Lett.  2002,  4 
• 8a Takahashi T. Kondakov DY. Suzuki N. Organometallics  1994,  13:  3411 
• 8b Campbell AD. Raynham TM. Taylor RJK. J. Chem. Soc., Perkin Trans. 1  2000,  3194 
• 9 Kocienski PJ. Pritchard M. Wadman SN. Whitby RJ. Yeates CL. J. Chem. Soc., Perkin Trans. 1  1992,  3419 
• 10 Negishi E. Cederbaum FE. Takahashi T. Tetrahedron Lett.  1986,  27:  2829 
• 11 Negishi E. Holmes SJ. Tour JM. Miller JA. Cederbaum FE. Swanson DR. Takahashi T. J. Am. Chem. Soc.  1989,  111:  3336 
• 12 Maye JP. Negishi E. Tetrahedron Lett.  1993,  34:  3359 
• 13 Wuvkulich PM. Uskovic MR. J. Org. Chem.  1982,  47:  1600 
• The only example of a 1,6-diene cocyclisation on zirconocene with control from a substituent adjacent to the ring junction was reported by Taber and gives exclusive 1,2-trans control:
• 15a Taber DF. Louey JP. Tetrahedron  1995,  51:  4495 
• There are many examples of trans 1,2-control in the cyclisation of enynes, e.g.:
• 15b Pagenkopf BL. Lund EC. Livinghouse T. Tetrahedron  1995,  51:  4421 
• 15c Agnel G. Owczarczyk Z. Negishi E. Tetrahedron Lett.  1992,  33:  1543 
• 16 Negishi EI. Maye JP. Choueiry D. Tetrahedron  1995,  51:  4447 
• 17 Yasuda H. Kajihara Y. Mashima K. Nagasawa K. Lee K. Nakamura A. Organometallics  1982,  1:  388 
• 18 Stothers JB. Carbon-13 NMR Spectroscopy   Academic Press; New York: 1972.  p.80-85  
• 19 Leigh WJ. Postigo JA. Zheng KC. Can. J. Chem.  1996,  74:  951 
• 20 Baldwin JE. Hofle GA. Lever OW. J. Am. Chem. Soc.  1974,  96:  7125 
• 21 Rousset CJ. Swanson DR. Lamaty F. Negishi E. Tetrahedron Lett.  1989,  30:  5105 
• 22 Kasatkin AN. Checksfield G. Whitby RJ. J. Org. Chem.  2000,  65:  3236 
• 23 Negishi E. Swanson DR. Cederbaum FE. Takahashi T. Tetrahedron Lett.  1987,  28:  917 
• 24 Takahashi T. Kageyama M. Denisov V. Hara R. Negishi E. Tetrahedron Lett.  1993,  34:  687 
• 25 Kemp MI. Whitby RJ. Coote SJ. Synthesis  1998,  552 
• 26 Miura K. Funatsu M. Saito H. Ito H. Hosomi A. Tetrahedron Lett.  1996,  37:  9059 
• 27 Urabe H. Hata T. Sato F. Tetrahedron Lett.  1995,  36:  4261 
• 28 Barluenga J. Sanz R. Fananas FJ. Chem. Eur. J.  1997,  3:  1324 
• 29 Takahashi T. Kotora M. Fischer R. Nishihara Y. Nakajima K. J. Am. Chem. Soc.  1995,  117:  11039 
• 30 Kemp MI. Whitby RJ. Coote SJ. Synthesis  1998,  557 
• 31a Gordon GJ. Luker T. Tuckett MW. Whitby RJ. Tetrahedron  2000,  56:  2113 
• 31b Dixon S. Fillery SM. Kasatkin A. Norton D. Thomas E. Whitby RJ. Tetrahedron  2004,  60:  1401 
• 32 Kasatkin A. Whitby RJ. J. Am. Chem. Soc.  1999,  121:  7039 
• 33 Perrin DD. Armarego WLF. Purification of Laboratory Chemicals   3rd ed.:  Pergamon; Oxford: 1988. 
• 34 Dessault PH. Zope UR. J. Org. Chem.  1995,  60:  8218 
• 35 Nonoshita K. Banno H. Maruko K. Yamamoto H. J. Am. Chem. Soc.  1990,  112:  316 
• 36 Bloodworth AJ. Courtneidge JL. Curtis RJ. Spencer MD. J. Chem. Soc., Perkin Trans. 1  1990,  2951 
• 37 Hartman GD. Halczenko W. Philips BT. J. Org. Chem.  1985,  50:  2427 
• 38 Pridgen LN. Snyder LJP. J. Org. Chem.  1989,  54:  1523 
• 39 Eriksson M. Iliefski T. Nilsson M. Olsson T. J. Org. Chem.  1997,  62:  182 
• 40 Barrot M. Fabrias G. Camps F. Tetrahedron  1994,  50:  9789 
• 41 Balzano F. Malanga C. Menicagli R. Synth. Commun.  1997,  27:  1509 
• 42 Bailey WF. Wachter-Jurcsak NM. Pineau MR. Ovaska TV. Warren RR. Lewis CE. J. Org. Chem.  1996,  61:  8216 
• 43 Kong J. White CA. Krylov AI. Sherrill D. Adamson RD. Furlani TR. Lee MS. Lee AM. Gwaltney SR. Adams TR. Ochsenfeld C. Gilbert ATB. Kedziora GS. Rassolov VA. Maurice DR. Nair N. Shao YH. Besley NA. Maslen PE. Dombroski JP. Daschel H. Zhang WM. Korambath PP. Baker J. Byrd EFC. Van Voorhis T. Oumi M. Hirata S. Hsu CP. Ishikawa N. Florian J. Warshel A. Johnson BG. Gill PMW. Head-Gordon M. Pople JA. J. Comp. Chem.  2000,  21:  1532 

14

Molecular modeling studies were performed with Spartan 04 (Wavefunction inc.). Conformational searches were carried out using molecular mechanics (MMFF94 force field extended to include transition metals, and cyclopentadiene ligands). Final minimizations of likely global minima were carried out using the hybrid DFT/HF B3LYP method using the 6-31G* basis set, and core electron approximation for zirconium. [43]