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. 2011 Apr 1;76(7):2350-4.
doi: 10.1021/jo200068q. Epub 2011 Mar 4.

Enhanced anti-diastereo- and enantioselectivity in alcohol-mediated carbonyl crotylation using an isolable single component iridium catalyst

Xin Gao  1 , Ian A Townsend, Michael J Krische
Affiliations

Enhanced anti-diastereo- and enantioselectivity in alcohol-mediated carbonyl crotylation using an isolable single component iridium catalyst

Xin Gao et al. J Org Chem. .

Abstract

The cyclometalated iridium complex (S)-I derived from [Ir(cod)Cl](2), 4-cyano-3-nitrobenzoic acid, allyl acetate, and (S)-SEGPHOS is conveniently isolated by precipitation or through conventional silica gel flash chromatography. This single-component precatalyst allows alcohol mediated carbonyl crotylations to be performed at significantly lower temperature, resulting in enhanced levels of anti-diastereo- and enantioselectivity. Most significantly, the chromatographically isolated precatalyst (S)-I enables carbonyl crotylations that are not possible under previously reported conditions involving in situ generation of (S)-I.

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Figures

Scheme 1
Scheme 1
Synthesis and isolation of the cyclometallated iridium complex (S)-I.
See this image and copyright information in PMC

References

    1. For selected reviews on C-C bond forming hydrogenation and transfer hydrogenation, see: Ngai M-Y, Kong JR, Krische MJ. J. Org. Chem. 2007;72:1063. Skucas E, Ngai M-Y, Komanduri V, Krische MJ. Acc. Chem. Res. 2007;40:1394. Shibahara F, Krische MJ. Chem. Lett. 2008;37:1102. Patman RL, Bower JF, Kim IS, Krische MJ. Aldrichim. Acta. 2008;41:95. Bower JF, Kim IS, Patman RL, Krische MJ. Angew. Chem. Int. Ed. 2009;48:34. Han SB, Kim IS, Krische MJ. Chem. Commun. 2009:7278.

    1. For enantioselective carbonyl allylation via iridium catalyzed C-C bond forming transfer hydrogenation and related processes, see: Kim IS, Ngai M-Y, Krische MJ. J. Am. Chem. Soc. 2008;130:6340. Kim IS, Ngai M-Y, Krische MJ. J. Am. Chem. Soc. 2008;130:14891. Kim IS, Han S-B, Krische MJ. J. Am. Chem. Soc. 2009;131:2514. Han SB, Kim I-S, Han H, Krische MJ. J. Am. Chem. Soc. 2009;131:6916. Lu Y, Kim I-S, Hassan A, Del Valle DJ, Krische MJ. Angew. Chem., Int. Ed. 2009;48:5018. Itoh J, Han SB, Krische MJ. Angew. Chem., Int. Ed. 2009;48:6313. Lu Y, Krische MJ. Org. Lett. 2009;11:3108. Hassan A, Lu Y, Krische MJ. Org. Lett. 2009;11:3112. Bechem B, Patman RL, Hashmi S, Krische MJ. J. Org. Chem. 2010;75:1795. Han SB, Han H, Krische MJ. J. Am. Chem. Soc. 2010;132:1760. Zhang YJ, Yang JH, Kim SH, Krische MJ. J. Am. Chem. Soc. 2010;132:4562. Han SB, Gao X, Krische MJ. J. Am. Chem. Soc. 2010;132:9153. Zbieg JR, Fukuzumi T, Krische MJ. Adv. Synth. Catal. 2010;352:2416. (n) For recent applications in total synthesis, see: Harsh P, O'Doherty GA. Tetrahedron. 2009;65:5051. Han SB, Hassan A, Kim I-S, Krische MJ. J. Am. Chem. Soc. 2010;132:15559.

    1. For selected reviews on enantioselective carbonyl allylation, see: Yamamoto Y, Asao N. Chem. Rev. 1993;93:2207. Ramachandran PV. Aldrichim. Acta. 2002;35:23. Kennedy JWJ, Hall DG. Angew. Chem. Int. Ed. 2003;42:4732. Denmark SE, Fu J. Chem. Rev. 2003;103:2763. Yu C-M, Youn J, Jung H-K. Bull. Korean Chem. Soc. 2006;27:463. Marek I, Sklute G. Chem. Commun. 2007:1683. Hall DG. Synlett. 2007:1644.

    1. For selected reviews of carbonyl allylation based on the reductive coupling of metallo-π-allyls derived from allylic alcohols, ethers or carboxylates, see: Masuyama Y. Palladium-Catalyzed Carbonyl Allylation via π-Allylpalladium Complexes. In: Liebeskind LS, editor. Advances in Metal-Organic Chemistry. Vol. 3. JAI Press; Greenwich: 1994. pp. 255–303. Tamaru Y. Palladium-Catalyzed Reactions of Allyl and Related Derivatives with Organoelectrophiles. In: Negishi E.-i., Meijere A. de., editors. Handbook of Organopalladium Chemistry for Organic Synthesis. Vol. 2. Wiley; New York: 2002. pp. 1917–1943. Tamaru Y. J. Organomet. Chem. 1999;576:215. Kondo T, Mitsudo T.-a. Curr. Org. Chem. 2002;6:1163. Tamaru Y. Eur. J. Org. Chem. 2005;13:2647. Zanoni G, Pontiroli A, Marchetti A, Vidari G. Eur. J. Org. Chem. 2007;22:3599.

    1. For selected examples of carbonyl allylation via catalytic Nozaki-Hiyama-Kishi coupling of allylic halides, see: Fürstner A, Shi N. J. Am. Chem. Soc. 1996;118:2533. Bandini M, Cozzi PG, Umani-Ronchi A. Polyhedron. 2000;19:537. McManus HA, Cozzi PG, Guiry PJ. Adv. Synth. Catal. 2006;348:551. Hargaden GC, Müller-Bunz H, Guiry PJ. Eur. J. Org. Chem. 2007:4235. Hargaden GC, O'Sullivan TP, Guiry PJ. Org. Biomol. Chem. 2008;6:562.

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