Synthesis, Table of Contents PAPER © Georg Thieme Verlag Stuttgart · New York Zirconium-Mediated Intramolecular Cyclization of Yne-Imine Muneyoshi Makabe, Yoshihiro Sato, Miwako Mori*Graduate School of Pharmaceutical Sciences, Hokkaido University, Sapporo 060-0812, Japane-Mail: mori@pharm.hokudai.ac.jp; Recommend Article Abstract Buy Article All articles of this category Abstract Successful zirconium-mediated intramolecular cyclization of yne-imine was achieved. When a crude imine, which was prepared from yne-aldehyde and primary amine in the presence of MgSO4, was treated with Cp2ZrBu2 at room temperature for several hours, a cyclopentane derivative was obtained in high yield. The intermediary azazirconacycle was treated with D3O+, I2 or t-BuNC to give the desired deuterated, iodinated or formylated product, respectively, at the vinyl position in good yield. Transmetalation of zirconacycle to CuCl was carried out and then allyl chloride was added to give an allylated compound in good yield. Selective bond fission of a zirconium-nitrogen bond of the azazirconacycle was achieved by treatment of the azazirconacycle with acyl halide to give an N-acylated vinylzirconium compound. Key words yne-imines - cyclization - zirconium Full Text References References 1 Negishi E. Cederbaum FE. Takahashi T. Tetrahedron Lett. 1986, 27: 2829 2a Negishi E. Acc. Chem. Res. 1987, 20: 65 2b Negishi E. Takahashi T. Synthesis 1988, 1 2c Nugent WA. Taber DF. J. Am. Chem. Soc. 1989, 11: 6435 2d Negishi E. Holmes SJ. Tour JM. Miller JA. Cederbaum FE. Swanson DR. Takahashi T. J. Am. Chem. Soc. 1989, 11: 3336 3a Nugent WA. Thorn DL. Harlow RL. J. Am. Chem. Soc. 1987, 109: 2788 3b Fagan PJ. Nugent WA. J. Am. Chem. Soc. 1988, 110: 2310 4a Rousset CJ. Swanson DR. Lamaty F. Negishi E. Tetrahedron Lett. 1989, 30: 5105 4b Nugent WA. Taber DF. J. Am. Chem. Soc. 1989, 11: 6435 4c Akita M. Yasuda H. Yamamoto H. Nakamura A. Polyhedron 1991, 10: 1 4d Mori M. Uesaka N. Shibasaki M. J. Org. Chem. 1992, 57: 3519 4e Maye JP. Negishi E. Tetrahedron Lett. 1993, 34: 3359 4f Mori M. Saitoh F. Uesaka N. Okamura K. Date T. J. Org. Chem. 1994, 59: 4993 4g Uesaka N. Saitoh F. Mori M. Shibasaki M. Okamura K. Date T. J. Org. Chem. 1994, 59: 5633 4h Mori M. Uesaka N. Saitoh F. Shibasaki M. J. Org. Chem. 1994, 59: 5643 4i Mori M. Imai AE. Uesaka N. Heterocycles 1995, 40: 551 4j Saitoh F. Mori M. Okamura K. Date T. Tetrahedron 1995, 51: 4439 4k Negishi E. Maye JP. Choueiry D. Tetrahedron 1995, 51: 4447 4l Taber DF. Louey JP. Tetrahedron 1995, 51: 4495 4m Mori M. Kuroda S. Zhang C.-S. Sato Y. J. Org. Chem. 1997, 62: 3263 5a Negishi E. Swanson DR. Cederbaum FE. Takahashi T. Tetrahedron Lett. 1987, 28: 917 5b Takahashi T. Swanson DR. Negishi E. Chem. Lett. 1987, 623 5c RajanBabu TV. Nugent WA. Taber DF. Fagan PJ. J. Am. Chem. Soc. 1988, 110: 7128 5d Lund EC. Livinghouse T. J. Org. Chem. 1989, 54: 4487 5e Mori M. Uesaka N. Shibasaki M. J. Chem. Soc., Chem. Commun. 1990, 1222 5f Wender PA. McDonald FE. Tetrahedron Lett. 1990, 31: 3691 5g Wender PA. McDonald FE. J. Am. Chem. Soc. 1990, 112: 4956 5h Agnel G. Negishi E. J. Am. Chem. Soc. 1991, 113: 7424 5i Agnel G. Owczarkzyk Z. Negishi E. Tetrahedron Lett. 1992, 33: 1543 5j Pagenkopf BL. Lund EC. Livinghouse T. Tetrahedron 1995, 51: 4421 5k Negishi E. Ma S. Sugihara T. Noda Y. J. Org. Chem. 1997, 62: 1922 6a Mori M. Uesaka N. Shibasaki M. J. Chem. Soc., Chem. Commun. 1989, 776 6b Takahashi T. Kageyama M. Denisov V. Hara R. Negishi E. Tetrahedron Lett. 1993, 34: 687 6c Hara R. Xi Z. Kotora M. Xi C. Takahashi T. Chem. Lett. 1996, 1003 6d Takahashi T. Xi C. Xi Z. Kageyama M. Fischer R. Nakajima K. Negishi E. J. Org. Chem. 1998, 63: 6802 7 Takahashi T. Tsai FY. Li Y. Nakajima K. Organometallics 2001, 20: 595 8 Jensen M. Livinghouse T. J. Am. Chem. Soc. 1989, 11: 4495 9a Davis JM. Whitby RJ. Tetrahedron Lett. 1992, 33: 5655 9b Davis JM. Whitby R. Jaxa-Chamiec A. Tetrahedron Lett. 1994, 35: 1445 9c Davis JM. Whitby R. Jaxa-Chamiec A. Synlett 1994, 110 9d Provert GD. Whitby RJ. Tetrahedron Lett. 1995, 36: 4113 10 In azatitanacyclobutene a similar result was obtained: McGrane PL. Jensen M. Livinghouse T. J. Am. Chem. Soc. 1992, 114: 5469
