Synthesis of Novel Steroid Backbones via Photoinduced Electron Transfer Initiated Domino Cyclizations of Silyl Enol Ethers

Jens O. Bunte; Stefanie Rinne; Jochen Mattay

doi:10.1055/s-2004-815956

FEATUREARTICLE

Synthesis of Novel Steroid Backbones via Photoinduced Electron Transfer Initiated Domino Cyclizations of Silyl Enol Ethers

Jens O. Bunte, Stefanie Rinne, Jochen Mattay*
Organische Chemie I, Fakultät für Chemie, Universität Bielefeld, Postfach 100131, 33501 Bielefeld, Germany
Fax: +49(521)1066417; e-Mail: mattay@uni-bielefeld.de ;

Abstract

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Abstract

Photoinduced electron transfer was used to activate silyl enol ethers. The generated radical cations of specifically designed precursors undergo ring closure reactions to yield novel steroid compounds. These domino reactions proceed with high stereoselectivity. The synthesis of the complex silyl enol ethers, the stereoselective domino cyclization process and the assignment of stereochemistry of the novel steroid compounds is presented.

Key words

domino reactions - cyclizations - stereoselectivity - electron transfer - steroids

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References

<A NAME="RT11703SS-1A">1a</A> Robinson R. J. Chem. Soc. 1917, 762

<A NAME="RT11703SS-1B">1b</A> Robinson R. J. Chem. Soc. 1917, 867

<A NAME="RT11703SS-1C">1c</A> Schöpf C. Lehmann G. Arnold W. Angew. Chem. 1937, 50: 779

<A NAME="RT11703SS-2A">2a</A> Tietze LF. Beifuss U. Angew. Chem. Int. Ed. 1993, 32: 131 ; Angew. Chem. 1993, 105, 137;

<A NAME="RT11703SS-2B">2b</A> Tietze LF. Chem. Rev. 1996, 96: 136

<A NAME="RT11703SS-2C">2c</A> Malacria M. Chem. Rev. 1996, 96: 306

<A NAME="RT11703SS-2D">2d</A> Hudlicky T. Chem. Rev. 1996, 96: 3

<A NAME="RT11703SS-3A">3a</A> Curran DP. Synthesis 1988, 417

<A NAME="RT11703SS-3B">3b</A> Curran DP. Synthesis 1988, 489

<A NAME="RT11703SS-3C">3c</A> Jasperse CP. Curran DP. Fevig TL. Chem. Rev. 1991, 91: 1237

<A NAME="RT11703SS-3D">3d</A> McCarroll AJ. Walton JC. Angew. Chem. Int. Ed. 2001, 40: 2224 ; Angew. Chem. 2001, 113, 2282

<A NAME="RT11703SS-4A">4a</A> Baguley PA. Walton JC. Angew. Chem. Int. Ed. 1998, 37: 3072 ; Angew. Chem. 1998, 110, 3272

<A NAME="RT11703SS-4B">4b</A> Snider BB. Chem. Rev. 1996, 96: 339

<A NAME="RT11703SS-4C">4c</A> Molander GA. Harris CR. Chem. Rev. 1996, 96: 307

<A NAME="RT11703SS-5A">5a</A> Kovarnos GJ. Turro NJ. Chem. Rev. 1986, 86: 401

<A NAME="RT11703SS-5B">5b</A> Mattay J. Vondenhof M. Top. Curr. Chem. 1991, 159: 219

<A NAME="RT11703SS-5C">5c</A> Kovarnos GJ. Fundamentals of Photoinduced Electron Transfer VCH Publishers; New York: 1993.

<A NAME="RT11703SS-5D">5d</A> Electron Transfer in Chemistry Vol. 1 and 2: Balzani V. Wiley-VCH; Weinheim: 2001.

<A NAME="RT11703SS-5E">5e</A> Heinemann C. Demuth M. J. Am. Chem. Soc. 1999, 121: 4894

<A NAME="RT11703SS-5F">5f</A> Hintz S. Heidbreder A. Mattay J. Top. Curr. Chem. 1996, 177: 77

<A NAME="RT11703SS-5G">5g</A> Oelgemöller M. Bunte JO. Mattay J. In Synthetic Organic Photochemistry Ramamurthy V. Schanze K. Marcel & Dekker; New York: in press

<A NAME="RT11703SS-6">6</A> Bunte JO. Mattay J. In CRC Handbook of Organic Photochemistry and Photobiology 2nd Ed.: Horspool WM. Lenci F. CRC Press; Boca Raton: 2004. Chap. 10.

<A NAME="RT11703SS-7A">7a</A> Ackermann L. Heidbreder A. Wurche F. Klärner F.-G. Mattay J. J. Chem. Soc., Perkin Trans. 2 1999, 863

<A NAME="RT11703SS-7B">7b</A> Hintz S. Mattay J. van Eldik R. Fu W.-F. Eur. J. Org. Chem. 1998, 1583

<A NAME="RT11703SS-7C">7c</A> Bunte JO. Rinne S. Schäfer C. Neumann B. Stammler H.-G. Mattay J. Tetrahedron Lett. 2003, 45

<A NAME="RT11703SS-8">8</A> Boehm HM. Handa S. Pattenden G. Roberts L. Blake AJ. Li WS. J. Chem. Soc., Perkin Trans. 1 2000, 3522

<A NAME="RT11703SS-9">9</A> Buchecker R. Marti U. Eugster CH. Helv. Chim. Acta 1982, 65: 896

<A NAME="RT11703SS-10A">10a</A> Johnson WS. Bartlett WR. Czeskis BA. Gautier A. Lee CH. Lemoine R. Leopold EJ. Luedtke GR. Bancroft KJ. J. Org. Chem. 1999, 64: 9587

<A NAME="RT11703SS-10B">10b</A> Brady SF. Ilton MA. Johnson WS. J. Am. Chem. Soc. 1968, 90: 2882

<A NAME="RT11703SS-11A">11a</A> Barco A. Benetti S. Pollini GP. Synthesis 1973, 316

<A NAME="RT11703SS-11B">11b</A> De Silva AN. Francis CL. Ward AD. Aust. J. Chem. 1993, 46: 1657

<A NAME="RT11703SS-12A">12a</A> Imamoto T. Comprehensive Organic Synthesis - Organocerium Reagents Vol. 1: Trost BM. Fleming I. Schreiber SL. Pergamon Press; Oxford: 1991. p.231

<A NAME="RT11703SS-12B">12b</A> Takeda N. Imamoto T. Org. Synth. 1999, 76: 228

<A NAME="RT11703SS-12C">12c</A> Panev S. Dimitrov V. Tetrahedron: Asymmetry 2000, 11: 1517

<A NAME="RT11703SS-13">13</A> Bergdahl M. Eriksson M. Nilsson M. Olsson T. J. Org. Chem. 1993, 58: 7238

<A NAME="RT11703SS-14">14</A> Bunte JO. PhD thesis Universität Bielefeld; Germany: 2003.

<A NAME="RT11703SS-15">15</A> Webster FX. Silverstein RM. Synthesis 1987, 922

<A NAME="RT11703SS-16A">16a</A> Johnstone RAW. Rose ME. Tetrahedron 1979, 35: 2169

<A NAME="RT11703SS-16B">16b</A> Giuliano RM. Jordan AD. Gauthier AD. Hoogsteen K. J. Org. Chem. 1993, 58: 4979

<A NAME="RT11703SS-17A">17a</A> Kikani BB. McKee JT. Zanger M. Synthesis 1990, 176

<A NAME="RT11703SS-17B">17b</A> Campaigne E. Selby TP. J. Heterocycl. Chem. 1980, 17: 1255

<A NAME="RT11703SS-17C">17c</A> Fuchs R. McGarrity JF. Synthesis 1992, 373

<A NAME="RT11703SS-17D">17d</A> Duc L. McGarrity JF. Meul T. Warm A. Synthesis 1992, 391

<A NAME="RT11703SS-18">18</A> Armarego WLF. Perrin DD. In Purification of Laboratory Chemicals 4th Ed.: Butterworth-Heinemann; Oxford: 1996.