Subscribe to RSS
DOI: 10.1055/s-2005-872097
Preparation and Reactions of Highly Functionalized Bis-Arylzinc Reagents Using a Li(acac)-Catalyzed Iodine-Zinc Exchange
Publication History
Publication Date:
22 July 2005 (online)
Abstract
Polyfunctional bis-arylzinc reagents are accessible via a new lithium acetylacetonate-catalyzed iodine-zinc exchange. This protocol tolerates sensitive functional groups (ketones, aldehydes or isothiocyanates) in the aryl iodides and allows the formation of highly functionalized zinc reagents. These zinc reagents can be used in a variety of catalyzed and uncatalyzed transformations.
Key words
functionalized zinc reagents - halogen-metal exchange - cross-coupling - nucleophilic catalysis
-
1a
Boudier A.Bromm LO.Lotz M.Knochel P. Angew. Chem. Int. Ed. 2000, 39: 4415 -
1b
Knochel P.Dohle W.Gommermann N.Kneisel FF.Kopp F.Korn T.Sapountzis I.Vu VA. Angew. Chem. Int. Ed. 2003, 42: 4302 -
2a
Nájera C.Sansano JM.Yus M. Tetrahedron 2003, 59: 9255 -
2b
Bailey WF.Patricia JJ. J. Organomet. Chem. 1988, 352: 1 -
2c
Bailey WF.Patricia JJ. J. Organomet. Chem. 1988, 352: 1 -
2d
Tucker CE.Majid TN.Knochel P. J. Am. Chem. Soc. 1992, 114: 3983 - For pioneering work, see:
-
2e
Wittig G.Pockels U.Dröge H. Ber. Dtsch. Chem. Ges. 1938, 71: 1903 -
2f
Wittig G.Schöllkopf U. Tetrahedron 1958, 3: 91 -
2g
Gilman H.Langham W.Jacoby AL. J. Am. Chem. Soc. 1939, 61: 106 -
2h
Jones RG.Gilman H. Org. React. 1951, 6: 339 -
3a
Abarbri M.Thibonnet J.Bérillon L.Dehmel F.Rottländer M.Knochel P. J. Org. Chem. 2000, 65: 4618 -
3b
Lee J.Velarde-Ortiz R.Guijarro A.Wurst JR.Rieke RD. J. Org. Chem. 2000, 65: 5428 -
3c
Kitagawa K.Inoue A.Shinokubo H.Oshima K. Angew. Chem. Int. Ed. 2000, 39: 2481 -
3d
Krasovskiy A.Knochel P. Angew. Chem. Int. Ed. 2004, 43: 3333 - 4
Piazza C.Knochel P. Angew. Chem. Int. Ed. 2002, 41: 3263 -
5a
Knochel P. Science of Synthesis Vol. 3:O’Neil I. Thieme; Stuttgart: 2004. p.5 -
5b
Knochel P.Millot N.Rodriguez AL.Tucker CA. Org. React. 2001, 58: 417 - 6
Bolm C.Hildebrand JP.Muniz K.Hermanns N. Angew. Chem. Int. Ed. 2001, 40: 3284 -
7a
Fillon H.Gosmini C.Périchon J. J. Am. Chem. Soc. 2003, 125: 3867 -
7b
Rieke RD. Science 1989, 246: 1260 -
7c
Zhu L.Wehmeyer RM.Rieke RD. J. Org. Chem. 1991, 56: 1445 -
7d
Uchiyama M.Koike M.Kameda M.Kondo Y.Sakamoto T. J. Am. Chem. Soc. 1996, 118: 8733 -
8a
Kneisel FF.Dochnahl M.Knochel P. Angew. Chem. Int. Ed. 2004, 43: 1017 -
8b
Gong LZ.Knochel P. Synlett 2005, 267 - 9
Knochel P.Yeh MCP.Berk SC.Talbert J. J. Org. Chem. 1988, 53: 2390 -
10a
Negishi E.Valente LF.Kobayashi M. J. Am. Chem. Soc. 1980, 102: 3298 -
10b
Kobayashi M.Negishi E. J. Org. Chem. 1980, 45: 5223 -
10c
Negishi E. Acc. Chem. Res. 1982, 15: 340 - 11
Boudier A.Darcel C.Flachsmann F.Micouin L.Oestreich M.Knochel P. Chem. Eur. J. 2000, 6: 2748 -
12a
Klement I.Rottländer M.Tucker CE.Majid TN.Knochel P.Venegas P.Cahiez G. Tetrahedron 1996, 52: 7201 -
12b
Staubitz A.Dohle W.Knochel P. Synthesis 2003, 233 - 13
Sessler JL.Wang B.Harriman A. J. Am. Chem. Soc. 1995, 117: 704 - 14 The alkynyl iodide 6 was obtained in two steps from commercially available 1-bromomethyl-2-iodobenzene in accordance to a literature procedure:
Bouyssi D.Balme G. Synlett 2001, 1191 - 15
Rao SA.Knochel P. J. Am. Chem. Soc. 1991, 113: 5735 - 16
Villiéras J.Rambaud M. Synthesis 1982, 924 - 17
Lin H.-S.Paquette LA. Synth. Commun. 1994, 24: 2503
References
The exact determination of all the concentrations of the solutions used (s-BuLi, ZnCl2, s-Bu2Zn) is decisive for the success of this procedure. Threefold titration and averaging have been typically done.
19The complete absence of LiCl is decisive for the success of the iodine-zinc exchange procedure.
20Threefold titration has been performed.
21Prepared by acylation of 4-hydroxy-3,5-diiodobenzoate with Ac2O (1.3 equiv) in pyridine in the presence of DMAP (0.1 equiv).