A Journey Across Recent Advances in Catalytic and Stereoselective Alkylation of Indoles

Marco Bandini; Alfonso Melloni; Simona Tommasi; Achille Umani-Ronchi

doi:10.1055/s-2005-865210

ACCOUNT

A Journey Across Recent Advances in Catalytic and Stereoselective Alkylation of Indoles

Marco Bandini*, Alfonso Melloni, Simona Tommasi, Achille Umani-Ronchi*
Dipartimento di Chimica ‘G. Ciamician’, Università di Bologna, via Selmi 2, 40126 Bologna, Italy
Fax: +39(051)2099456; e-Mail: marco.bandini@unibo.it; e-Mail: achille.umanironchi@unibo.it;

Abstract

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Abstract

In this Account our recent results in relation to the catalytic and stereoselective Friedel-Crafts (FC) alkylation of indoles are described. Over the last decade, remarkable efforts have been devoted towards the replacement of the primal approaches with new more efficient, reliable, and environmentally benign strategies for the functionalization of indoles. Moreover, the emerging area of catalytic asymmetric FC processes is addressed and some examples of enantioselective alkylations of indoles via 1,4-addition to α,β-unsaturated systems and asymmetric ring-opening reaction of aromatic epoxides are described.

1 Introduction
2 Catalytic Regioselective Alkylation of Indoles
2.1 Michael Addition of Indoles to Enones Catalyzed by InBr₃
2.2 Synthesis of 1,3-Bisindolyl Ketones through 1,4-Conjugate Addition of Indoles to Indolyl Enones
2.3 Synthesis of 1,2,3,4-Tetrahydro-β-carbolines and Pyranyl Analogues via Intramolecular Indole Alkylation
2.4 InBr₃-Catalyzed Michael Addition of Indoles to Nitroalkenes in Aqueous Media
2.5 Environmentally Benign Continuous and Semi-continuous Solid-Acid-Catalyzed Alkylation of Indoles
2.6 Regio- and Stereoselective Catalyzed Ring Opening of Enantiomerically Pure Aromatic Epoxides
2.7 Pd-Catalyzed Allylic Alkylation of Indoles
3 Catalytic and Enantioselective Alkylation of Indoles: Introduction.
3.1 BINAP-Pd(II) as a Chiral Lewis Acid for the Michael Addition of Indoles to α,β-Unsaturated Thioesters
3.2 [SalenAlCl] as the Catalyst for the Enantioselective Addition of Indoles to Enones
3.3 Asymmetric Kinetic Resolution of Racemic Internal Aromatic Epoxides Promoted by [SalenCrX]
4 Outlook

Key words

alkylations - asymmetric catalysis - electrophilic aromatic substitutions - indoles - Lewis acids

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Referenzen

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<A NAME="RA36904ST-81C">81c</A> Bartoli G. Bosco M. Carlone A. Locatelli M. Massaccesi M. Melchiorre P. Sambri L. Org. Lett. 2004, 6: 2173

<A NAME="RA36904ST-81D">81d</A> Bartoli G. Bosco M. Carlone A. Locatelli M. Melchiorre P. Sambri L. Org. Lett. 2004, 6: 3973

<A NAME="RA36904ST-81E">81e</A> Ready JM. Jacobsen EN. J. Am. Chem. Soc. 1999, 121: 6086

<A NAME="RA36904ST-82A">82a</A> Bandini M. Cozzi PG. Melchiorre P. Umani-Ronchi A. Angew. Chem. Int. Ed. 1999, 38: 3357

<A NAME="RA36904ST-82B">82b</A> Bandini M. Cozzi PG. Melchiorre P. Morganti S. Umani-Ronchi A. Org. Lett. 2001, 3: 1153

<A NAME="RA36904ST-83">83</A> Bandini M. Cozzi PG. Melchiorre P. Umani-Ronchi A. Angew. Chem. Int. Ed. 2004, 43: 84

TMSN₃:

<A NAME="RA36904ST-84A">84a</A> Yamashita H. Bull. Chem. Soc. Jpn. 1988, 61: 1213

<A NAME="RA36904ST-84B">84b</A> See also: Nugent WA. J. Am. Chem. Soc. 1992, 114: 2768

<A NAME="RA36904ST-84C">84c</A> See also: Martinez LE. Leighton JL. Carsten DH. Jacobsen EN. J. Am. Chem. Soc. 1995, 117: 5897

12-Halohydrins:

<A NAME="RA36904ST-85A">85a</A> Denmark SE. Barsanti PA. Wong KT. Stavenger RA. J. Org. Chem. 1998, 63: 2428

<A NAME="RA36904ST-85B">85b</A> Nugent WA. J. Am. Chem. Soc. 1998, 120: 7139

<A NAME="RA36904ST-85C">85c</A> Tao B. Lo MMC. Fu GC. J. Am. Chem. Soc. 2001, 123: 353

<A NAME="RA36904ST-85D">85d</A> Nakajima M. Saito M. Uemura M. Hashimoto S. Tetrahedron Lett. 2002, 43: 8827

TMSCN:

<A NAME="RA36904ST-86A">86a</A> Cole MB. Shimizu KD. Krueger CA. Harrity JPA. Snapper ML. Hoveyda AH. Angew. Chem., Int. Ed. Engl. 1996, 35: 1668

<A NAME="RA36904ST-86B">86b</A> Shimizu K. Cole BM. Krueger CA. Kuntz KW. Snapper ML. Hoveyda AH. Angew. Chem., Int. Ed. Engl. 1997, 36: 1703

<A NAME="RA36904ST-86C">86c</A> Schaus SE. Jacobsen EN. Org. Lett. 2000, 2: 1001

ROH:

<A NAME="RA36904ST-87A">87a</A> Jacobsen EN. Kakiuchi F. Konsler RG. Larrow JF. Tokunaga M. Tetrahedron Lett. 1997, 38: 773

<A NAME="RA36904ST-87B">87b</A> Matsunaga S. Das J. Roels J. Vogl EM. Yamamoto N. Iida T. Yamaguchi K. Shibasaki M. J. Am. Chem. Soc. 2000, 122: 2252

RSH:

<A NAME="RA36904ST-88A">88a</A> Iida T. Yamamoto T. Sasai H. Shibasaki M. J. Am. Chem. Soc. 1997, 119: 4783

<A NAME="RA36904ST-88B">88b</A> Wu MH. Jacobsen EN. J. Org. Chem. 1998, 63: 5252

<A NAME="RA36904ST-88C">88c</A> Wu J. Hou X.-L. Dai L.-X. Xia L.-J. Tang M.-H. Tetrahedron: Asymmetry 1998, 9: 3431

<A NAME="RA36904ST-89">89</A> RNH₂: Shneider C. Sreekanth AR. Mai E. Angew. Chem. Int. Ed. 2004, 43: 5691

ZnR₂:

<A NAME="RA36904ST-90A">90a</A> Baldassi F. Crotti P. Macchia F. Pineschi M. Arnold A. Feringa BL. Tetrahedron Lett. 1998, 39: 7795

<A NAME="RA36904ST-90B">90b</A> Bertozzi F. Crotti P. Macchia F. Pineschi M. Arnold A. Feringa BL. Org. Lett. 2000, 2: 933

<A NAME="RA36904ST-90C">90c</A> Lautens M. Renaud J.-L. Hiebert S. J. Am. Chem. Soc. 2000, 122: 1804

<A NAME="RA36904ST-91">91</A> RB(OH)₂: Lautens M. Dockendorff C. Fagnou K. Malicki A. Org. Lett. 2002, 4: 1311