Carbohydrate-Based Tolylsulfonyl Hydrazines: Effective Catalysts for Michael Addition of Indoles to Electron-Deficient Olefins in Water

Abstract

Carbohydrate-based tolylsulfonyl hydrazines were used for the first time to catalyze the Michael reaction of indoles to electron-deficient olefins in aqueous media to afford 3-substituted indole derivatives in good to excellent yields at room temperature.

Key words

carbohydrate-based tolylsulfonyl hydrazines - catalyst - Michael addition of indole - water

References and Notes

• 1a Li C.-J. Chem. Rev.  2005,  105:  3095 
• 1b Lindström UM. Chem. Rev.  2002,  102:  2751 
• 1c Kobayashi S. Manabe K. Acc. Chem. Res.  2002,  35:  209 
• 2a Dalko PI. Moisan L. Angew. Chem. Int. Ed.  2004,  43:  5138 
• 2b List B. Acc. Chem. Res.  2004,  37:  548 
• For examples, see:
• 3a Cheng L. Wu X. Lu Y. Org. Biomol. Chem.  2007,  5:  1018 
• 3b Mase N. Nakai Y. Ohara N. Yoda H. Takabe K. Tanaka F. Barbas CF. J. Am. Chem. Soc.  2006,  128:  734 
• 3c Luo S. Mi X. Liu S. Cheng J.-P. Chem. Commun.  2006,  3687 
• 3d Torii H. Nakadai M. Ishihara K. Saito S. Yamamoto H. Angew. Chem. Int. Ed.  2004,  43:  1983 
• 3e Hamada T. Manabe K. Kobayashi S. J. Am. Chem. Soc.  2004,  126:  7768 
• 3f Dickerson TJ. Janda KD. J. Am. Chem. Soc.  2002,  124:  3220 
• 3g Córdova A. Notz W. Barbas CF. Chem. Commun.  2002,  3024 
• 4 Movassaghi M. Jacobsen EN. Science  2002,  298:  1904 
• 5a Gribble GW. J. Chem. Soc., Perkin Trans. 1  2000,  1045 
• 5b Moore RE. Cheuk C. Yang XQ. Patterson GML. Bonjouklian R. Smitka TA. Mynderse JS. Foster RS. Jones ND. Swartzendruber JK. Deeter JB. J. Org. Chem.  1987,  52:  1036 
• 5c Moore RE. Cheuk C. Patterson GML. J. Am. Chem. Soc.  1984,  106:  6456 
• 6a An L.-T. Zou J.-P. Zhang L.-L. Zhang Y. Tetrahedron Lett.  2007,  48:  4297 
• 6b Azizi N. Arynasab F. Saidi MR. Org. Biomol. Chem.  2006,  4:  4275 
• 6c Zhou W. Xu L.-W. Li L. Yang L. Xia C.-G. Eur. J. Org. Chem.  2006,  5225 
• 6d Lin C. Hsu J. Sastry MNV. Fang H. Tu Z. Liu J.-T. Yao C.-F. Tetrahedron  2005,  61:  11751 
• 7a Tabatabaeian K. Mamaghani M. Mahmoodi NO. Khorshidi A. J. Mol. Catal. A: Chem.  2007,  270:  112 
• 7b Jia Y.-X. Zhu S.-F. Yang Y. Zhou Q.-L. J. Org. Chem.  2006,  71:  75 
• 7c Bartoli G. Bosco M. Giuli S. Giuliani A. Lucarelli L. Marcantoni E. Sambri L. Torregiani E. J. Org. Chem.  2005,  70:  1941 
• 7d Komoto I. Kobayashi S. J. Org. Chem.  2004,  69:  680 
• 8a Firouzabadi H. Iranpoor N. Nowrouzi F. Chem. Commun.  2005,  789 
• 8b Manabe K. Aoyama N. Kobayashi S. Adv. Synth. Catal.  2001,  343:  174 
• 9a Deng D.-S. Liu P. Cai J. Eur. J. Org. Chem.  2007,  1594 
• 9b Deng D.-S. Cai J. Helv. Chim. Acta  2007,  90:  114 
• 9c Wu Y. Chen Y. Deng D.-S. Cai J. Synlett  2005,  1627 
• 9d Wu Y.-S. Cai J. Hu Z.-Y. Liu G.-X. Tetrahedron Lett.  2004,  45:  8949 
• 10 Ojala WH. Ojala CH. Gleason WB. J. Chem. Crystallogr.  1999,  29:  19 

11

Typical Experimental Procedure: A mixture of the olefin (1 mmol) and catalyst 1 (0.1 mmol) in H₂O (1 mL) was treated with indole (2 mmol). The resulting suspension was stirred at r.t. and the reaction was monitored by TLC until the starting material was consumed. The mixture was quenched with a sat. aq NaCl solution and then extracted with EtOAc (3 × 20 mL). The organic layers were combined and washed with brine, and dried over anhyd MgSO₄. The solvent was removed in vacuo to yield the crude product. Purification by silica gel chromatography using 100-200 mesh ZCX II eluted with hexane-EtOAc (5:1) afforded the Michael product.