Synlett, Table of Contents LETTER © Georg Thieme Verlag Stuttgart · New York Intramolecular Chromium(II)-Catalyzed Pinacol Cross Coupling of 2-Methylene-α,ω-dicarbonyls [1] Ulrich Groth*, Marc Jung, Till VogelFachbereich Chemie, Universität Konstanz, Fach M-720, Universitätsstr. 10, 78457 Konstanz, GermanyFax: +49(7531)884155; e-Mail: Ulrich.Groth@uni-konstanz.de; Recommend Article Abstract Buy Article All articles of this category Abstract Using only 10% of CrCl2 as catalyst, manganese-powder as reducing agent and TMSCl as scavenger, 2-methylene-α,ω-dialdehydes and -ketones can be coupled to form cyclic diols diastereoselectively. The diastereomeric excess strongly depends on the ring size and the substituents of the ω-carbonyl group. The greater the ring size the higher diastereoselectivities are observed. In all cases cis-diols are preferentially formed. Key words chromium - catalysis - cross-coupling - cyclizations - pinacols Full Text References References 1 Transition Metal Catalyzed Reactions in Organic Synthesis, part VII. For part VI see: Eckenberg P. Groth U. Synlett 2003, 2188 For reviews see: 2a Kropf H. Thiem J. Methoden der Organischen Chemie (Houben-Weyl) Vol. 6/1a/1: Müller E. Thieme Verlag; Stuttgart: 1984. p.592 2b Kolb HC. van Nieuwenhze MS. Sharpless KB. Chem. Rev. 1994, 94: 2483 2c Becker H. Sharpless KB. Angew. Chem., Int. Ed. Engl. 1996, 35: 448 For reviews see: 3a Kropf H. Thiem J. Methoden der Organischen Chemie (Houben-Weyl) Vol. 6/1a/2: Müller E. Thieme Verlag; Stuttgart: 1984. p.1485 3b Robertson GM. Comprehensive Organic Synthesis Vol. 3: Trost BM. Flemming I. Pattenden G. Pergamon; Oxford: 1991. p.563 3c Fürstner A. Csuk R. Rohrer C. Weidmann H. J. Chem. Soc., Perkin Trans. 1 1988, 1729 3d Fürstner A. Bogdanovic B. Angew. Chem., Int. Ed. Engl. 1996, 35: 2442 3e Wirth T. Angew. Chem., Int. Ed. Engl. 1996, 35: 61 3f Gansäuer A. Bluhm H. Chem. Rev. 2000, 100: 2771 4 Kammermeier B. Beck G. Jacobi D. Jendralla H. Angew. Chem., Int. Ed. Engl. 1994, 33: 685 See ref.6 and: 5a Nazare M. Waldmann H. Angew. Chem. Int. Ed. 2000, 39: 1125 5b Nazare M. Waldmann H. Chem.-Eur. J. 2001, 7 (15): 3363 6a Nicolaou KC. Yang Z. Liu JJ. Ueno H. Nantermet PG. Guy RK. Clairborn CF. Renaud J. Couladouros EA. Paulvannan K. Sorensen EJ. J. Am. Chem. Soc. 1995, 117: 634 6b Shiina I. Nishimura T. Ohkawa N. Sakoh H. Nishimura K. Saitoh K. Mukaiyama T. Chem. Lett. 1997, 419 7a Sassa T. Tojyo T. Munakata K. Nature 1970, 227: 379 7b Takeshita H. Kato N. Nakanishi K. Tagoshi H. Hatsui T. Chem. Lett. 1984, 1495 7c Kato N. Takeshita H. Bull. Chem. Soc. Jpn. 1985, 59: 1109 7d Okamoto H. Arita H. Kato N. Takeshita H. Chem. Lett. 1994, 2335 7e Kato N. Okamato H. Takeshita H. Tetrahedron 1996, 52: 3921 7f Mehta G. Singh V. Chem. Rev. 1999, 99: 881 8a SmI2/Mg: Nomura R. Matsuno T. Endo T. J. Am. Chem. Soc. 1996, 118: 11666 8b (EBTHI)TiCl2/Zn: Gansäuer A. Synlett 1997, 363 8c Cp2TiCl2/Zn: Gansäuer A. Chem. Commun. 1997, 457 8d Cp2TiCl2/Mn: Gansäuer A. Bauer D. J. Org. Chem. 1998, 63: 2070 8e CpV(CO)4/Zn/Me3SiCl: Hirao T. Hasegawa T. Muguruma Y. Ikeda I. J. Org. Chem. 1996, 61: 366 8f CrCl2/Mn: Svato A. Boland W. Synlett 1998, 548 8g Cp2Ti(Ph)Cl/Zn: Yamamoto Y. Hattori R. Itoh K. Chem. Commun. 1999, 825 8h Ce(i-PrO)3/Et2Zn: Groth U. Jeske M. Angew. Chem. Int. Ed. 2000, 39: 574 8i Ce(t-BuO)3/Mg, Zn, Mn: Groth U. Jeske M. Synlett 2001, 129 9a Takai K. Morita R. Toratsu C. Angew. Chem. Int. Ed. 2001, 40: 1116 9b Takai K. Morita R. Matsushita H. Toratsu C. Chirality 2003, 15: 17 10 Jung M. Groth U. Synlett 2002, 2015 11a Fürstner A. Shi N. J. Am. Chem. Soc. 1996, 118: 2533 11b Fürstner A. Shi N. J. Am. Chem. Soc. 1996, 118: 12349 12 Claus RE. Schreiber SL. Org. Synth. 1985, 64: 150 13 According to: Takano S. Inomata K. Samizu K. Tomita S. Yanase M. Suzuki M. Iwabuchi Y. Sugihara T. Ogasawara K. Chem. Lett. 1989, 1283 14 Kinast G. Tieze L.-F. Angew. Chem., Int. Ed. Engl. 1976, 15: 239 15a Dess DB. Martin JC. J. Org. Chem. 1983, 48: 4155 15b Dess DB. Martin JC. J. Am. Chem.Soc. 1991, 113: 7277 15c Ireland RE. Liu L. J. Org. Chem. 1993, 58: 2899 15d Meyer SD. Schreiber SL. J. Org. Chem. 1994, 59: 7549 15e Speicher A. Bromm V. Eicher T. J. Prakt. Chem. 1996, 338: 588 16 According to: van Rheenen V. Cha DY. Hartley WM. Org. Synth., Coll. Vol. 6 Wiley; New York: 1988. p.342 17 According to: Pine SH. Shen GS. Hoang H. Synthesis 1991, 165
