Catalytic Epoxypolyene Cyclization via Radicals: A Simple Total Synthesis of Sclareol Oxide and its 8-Epimer

Andreas Gansäuer; Dennis Worgull; José Justicia

doi:10.1055/s-2006-942406

PAPER

Catalytic Epoxypolyene Cyclization via Radicals: A Simple Total Synthesis of Sclareol Oxide and its 8-Epimer

Andreas Gansäuer*, Dennis Worgull, José Justicia
Kekulé-Institut für Organische Chemie und Biochemie der Universität Bonn, Gerhard-Domagk-Str. 1, 53121 Bonn, Germany
Fax: +49(228)734760; e-Mail: andreas.gansaeuer@uni-bonn.de;

Abstract

All articles of this category

Abstract

A short synthesis of sclareol oxide from epoxyfarnesyl acetone in six steps is described. The strategy features a titanocene-catalyzed epoxypolyene cyclization for the construction of the carbocyclic core structure. The exo olefin formed during the termination of the cyclization is essential for the ensuing functional group modification that results in the preparation of the dihydropyran.

Key words

catalysis - epoxypolyene cyclization - natural products - radicals - titanocene

Full Text

References

<A NAME="RC02506SS-1">1</A> Pitarokili D. Couladis M. Petsikos-Panayotarou N. Tzakou O. J. Agric. Food Chem. 2002, 50: 6688

<A NAME="RC02506SS-2">2</A> Barrero AF. Álvarez-Manzaneda EJ. Altarejos J. Salido S. Ramos JM. Tetrahedron 1993, 49: 10405

<A NAME="RC02506SS-3">3</A> Gao X. Matsuo Y. Snider BB. Org. Lett. 2006, 8: 2123

<A NAME="RC02506SS-4A">4a</A> Castro JM. Salido S. Altarejos J. Nogueras M. Sánchez A. Tetrahedron 2002, 58: 5941

<A NAME="RC02506SS-4B">4b</A> Moulines J. Bats J.-P. Lamidey A.-M. Da Silva N. Helv. Chim. Acta 2004, 87: 2695

<A NAME="RC02506SS-5A">5a</A> Vidari G. Dapiaggi A. Zanoni G. Garlaschelli L. Tetrahedron Lett. 1993, 34: 6485

<A NAME="RC02506SS-5B">5b</A> Corey EJ. Noe MC. Lin S. Tetrahedron Lett. 1995, 36: 8741

<A NAME="RC02506SS-6A">6a</A> Nugent WA. RajanBabu TV. J. Am. Chem. Soc. 1988, 110: 8561

<A NAME="RC02506SS-6B">6b</A> RajanBabu TV. Nugent WA. J. Am. Chem. Soc. 1994, 116: 986

<A NAME="RC02506SS-6C">6c</A> Gansäuer A. Pierobon M. Bluhm H. Angew. Chem. Int. Ed. 1998, 37: 101

<A NAME="RC02506SS-6D">6d</A> Gansäuer A. Bluhm H. Pierobon M. J. Am. Chem. Soc. 1998, 120: 12849

<A NAME="RC02506SS-6E">6e</A> Gansäuer A. Lauterbach T. Bluhm H. Noltemeyer M. Angew. Chem. Int. Ed. 1999, 38: 2909

<A NAME="RC02506SS-6F">6f</A> Gansäuer A. Bluhm H. Chem. Rev. 2000, 100: 2771

<A NAME="RC02506SS-6G">6g</A> Gansäuer A. Pierobon M. Bluhm H. Angew. Chem. Int. Ed. 2002, 41: 3206

<A NAME="RC02506SS-6H">6h</A> Gansäuer A. Rinker B. Pierobon M. Grimme S. Gerenkamp M. Mück-Lichtenfeld C. Angew. Chem. Int. Ed. 2003, 42: 3687

<A NAME="RC02506SS-6I">6i</A> Gansäuer A. Lauterbach T. Narayan S. Angew. Chem. Int. Ed. 2003, 42: 5556

<A NAME="RC02506SS-6J">6j</A> Gansäuer A. Lauterbach T. Geich-Gimbel D. Chem. Eur. J. 2004, 10: 4983

<A NAME="RC02506SS-6K">6k</A> Friedrich J. Dolg M. Gansäuer A. Geich-Gimbel D. Lauterbach T. J. Am. Chem. Soc. 2005, 127: 7071

<A NAME="RC02506SS-6L">6l</A> Daasbjerg K. Svith H. Grimme S. Gerenkamp M. Mück-Lichtenfeld C. Gansäuer A. Barchuk A. Keller F. Angew. Chem. Int. Ed. 2006, 45: 2041

<A NAME="RC02506SS-7A">7a</A> Justicia J. Rosales A. Buñuel E. Oller-López JL. Valdivia M. Haïdour A. Oltra JE. Barrero AF. Cárdenas DJ. Cuerva JM. Chem. Eur. J. 2004, 10: 1778

<A NAME="RC02506SS-7B">7b</A> Justicia J. Oltra JE. Cuerva JM. J. Org. Chem. 2004, 69: 5803

<A NAME="RC02506SS-7C">7c</A> Justicia J. Oller-López JL. Campaña AG. Oltra JE. Cuerva JM. Buñuel E. Cárdenas DJ. J. Am. Chem. Soc. 2005, 127: 14911

<A NAME="RC02506SS-7D">7d</A> Cuerva JM. Justicia J. Oller-López JL. Oltra JE. Top. Curr. Chem. 2006, 264: 63

<A NAME="RC02506SS-8A">8a</A> Abe I. Rohmer M. Prestwich GD. Chem. Rev. 1993, 93: 2189

<A NAME="RC02506SS-8B">8b</A> Wendt KU. Schulz GE. Corey EJ. Liu DR. Angew. Chem. Int. Ed. 2000, 39: 2812

<A NAME="RC02506SS-8C">8c</A> Yoder RA. Johnston JN. Chem. Rev. 2005, 105: 4730

<A NAME="RC02506SS-9">9</A> Gansäuer A. Rosales A. Justicia J. Synlett 2006, 927

<A NAME="RC02506SS-10">10</A> Gopalan A. Prieto R. Mueller B. Peters D. Tetrahedron Lett. 1992, 33: 1679

<A NAME="RC02506SS-11">11</A> van Tamelen EE. Storni A. Hessler EJ. Schwartz M. J. Am. Chem. Soc. 1963, 85: 3295

<A NAME="RC02506SS-12A">12a</A> Barton DHR. Ferreira JA. Jaszberenyi JC. Free Radical Deoxygenation of Thiocarbonyl Derivatives of Alcohols, In Preparative Carbohydrate Chemistry Hanessian S. Marcel Dekker; New York: 1997. 15-172:

<A NAME="RC02506SS-12B">12b</A> Zard SZ. Xanthates and Related Derivatives as Radical Precursors, In Radicals in Organic Synthesis Vol. 1: Wiley-VCH; Weinheim: 2001. 90-108:

<A NAME="RC02506SS-12C">12c</A> Crich D. Quintero L. Chem. Rev. 1989, 89: 1413

<A NAME="RC02506SS-13">13</A> Still WC. Kahn A. Mitra A. J. Org. Chem. 1978, 43: 2923

<A NAME="RC02506SS-14">14</A> Barrero AF. Cuerva JM. Herrador MM. Valdivia MV. J. Org. Chem. 2001, 66: 4074

<A NAME="RC02506SS-15">15</A> Matres P. Perfetti P. Zahra JP. Waegell B. Tetrahedron Lett. 1991, 32: 765