Palladium-Catalyzed Asymmetric Suzuki–Miyaura Cross Coupling with Homochiral Phosphine Ligands Having Tetrahydro-1H-imidazo[1,5-a]indole Backbone

The authors would like to dedicate this article to Professor Dieter Enders on the occasion of his 70^th birthday.

Abstract

Amphiphilic polystyrene-poly(ethylene glycol) resin-supported chiral imidazoindole phosphines (PS-PEG-L*), (3R,9aS)-2-aryl-3-(2-dialkylphosphino)phenyltetrahydro-1H-imidazo[1,5-a]indol-1-one, bearing PPh₂, P(t-Bu)₂, and P(c-Hex)₂ groups were designed and prepared with a view toward using them in aqueous heterogeneous asymmetric Suzuki–Miyaura biaryl coupling. The asymmetric coupling of 2-substituted 1-iodonaphthalenes and 2-substituted naphthalen-1-ylboronic acid took place in water under heterogeneous conditions in the presence of 10 mol% palladium of PS-PEG-L*-Pd complexes to give up to 94% ee of (S)-2,2′-disubstituted 1,1′-binaphthyls.

Key words

asymmetric catalysis - biaryls - cross-coupling - palladium - Suzuki–Miyaura coupling - catalysis in water - heterogeneous catalysis

• References


For reviews, see:
• 1a Uozumi Y. Top. Curr. Chem. 2004; 242: 77
• 1b Uozumi Y. Heterogeneous Asymmetric Catalysis in Aqueous Media. In Handbook of Asymmetric Heterogeneous Catalysis. Ding K, Uozumi Y. Wiley-VCH; Weinheim: 2008. Chap. 6
• 1c Uozumi Y. Bull. Chem. Soc. Jpn. 2008; 81: 1183

Alkylation:
• 2a Uozumi Y, Shibatomi K. J. Am. Chem. Soc. 2001; 123: 2919

Amination:
• 2b Uozumi Y, Tanaka H, Shibatomi K. Org. Lett. 2004; 6: 281

Cyclization:
• 2c Nakai Y, Uozumi Y. Org. Lett. 2005; 7: 291

Etherification:
• 2d Uozumi Y, Kimura M. Tetrahedron: Asymmetry 2006; 17: 161

Nitromethylation:
• 2e Uozumi Y, Suzuka T. J. Org. Chem. 2006; 71: 8644

Enantio­selective desymmetrization:
• 2f Uozumi Y, Takenaka H, Suzuka T. Synlett 2008; 1557
• 2g Uozumi Y. Pure Appl. Chem. 2007; 79: 1481
• 3 Uozumi Y, Matsuura Y, Arakawa T, Yamada YM. A. Angew. Chem. Int. Ed. 2009; 48: 2708

For nonasymmetric Suzuki–Miyaura coupling in water with PS-PEG resin-supported Pd complexes, see:
• 4a Uozumi Y, Danjo H, Hayashi T. J. Org. Chem. 1999; 64: 3384
• 4b Uozumi Y, Nakai Y. Org. Lett. 2002; 4: 2997
• 4c Uozumi Y, Kikuchi M. Synlett 2005; 1775
• 5 Shibatomi K, Uozumi Y. Tetrahedron: Asymmetry 2002; 13: 1769

For recent reviews, see:
• 6a Hartwig JF. Acc. Chem. Res. 2008; 41: 1534
• 6b Surry DS, Buchwald SL. Angew. Chem. Int. Ed. 2008; 47: 6338
• 6c Martin R, Buchwald SL. Acc. Chem. Res. 2008; 41: 1461

For pioneering studies on the asymmetric Suzuki–Miyaura coupling, see:
• 7a Uemura M, Nishimura H, Hayashi T. Tetrahedron Lett. 1993; 34: 107
• 7b Cho SY, Shibasaki M. Tetrahedron: Asymmetry 1998; 9: 3751
• 7c Cammidge AN, Crépy KV. L. Chem. Commun. 2000; 1723

For a review on asymmetric cross-coupling, see:
• 8a Uozumi Y. Carbon–Carbon Bond Forming Reactions via Cross-Coupling . In Comprehensive Chirality . Carreira EM, Yamamoto H. Elsevier; Amsterdam: 2012. Chap. 4.3, 18-32
• 8b Zhang D, Wang Q. Coord. Chem. Rev. 2015; 286: 1

For examples for highly stereoselective Suzuki–Miyaura coupling, see:
• 9a Yin J, Buchwald SL. J. Am. Chem. Soc. 2000; 122: 12051
• 9b Genov M, Almorin P, Espinet P. Chem. Eur. J. 2006; 12: 9346
• 9c Bermejo A, Fernández R, Lassaletta JM. J. Am. Chem. Soc. 2008; 130: 15798
• 9d Shen X, Jones GO, Watson DA, Bhayana B, Buchwald SL. J. Am. Chem. Soc. 2010; 132: 11278
• 9e Zhang S.-S, Wang Z.-Q, Xu M.-H, Lin G.-Q. Org. Lett. 2010; 12: 5546
• 9f Yamamoto T, Akai Y, Nagata Y, Suginome M. Angew. Chem. Int. Ed. 2011; 50: 8844
• 9g Wang S, Li J, Miao T, Wu W, Li Q, Zhuang Y, Zhou Z, Qiu L. Org. Lett. 2012; 14: 1966
• 9h Tang W, Patel ND, Xu G, Xu X, Savoie J, Ma S, Hao M.-H, Keshipeddy S, Capacci AG, Wei X, Zhang Y, Gao JJ, Li W, Rodriguez S, Lu BZ, Yee NK, Senanayake CH. Org. Lett. 2012; 14: 2258
• 9i Zhou Y, Wang S, Wu W, Li Q, He Y, Zhuang Y, Li L, Pang J, Zhou Z, Qiu L. Org. Lett. 2013; 15: 5508
• 9j Ros A, Estepa B, Bermejo A, Alvarez E, Fernandez R, Lassaletta JM. J. Org. Chem. 2012; 77: 4740
• 9k Xu G, Fu W, Liu G, Senanayake CH, Tang W. J. Am. Chem. Soc. 2014; 136: 570
• 9l Akai Y, Konnert L, Yamamoto T, Suginome M. Chem. Commun. 2015; 51: 7211
• 10a Bayer E, Rapp W In Chemistry of Peptides and Proteins . Vol. 3. Voelter W, Bayer E, Ovchinikov YA, Iwanov VT. Walter de Gruyter; Berlin: 1986: 3
• 10b Rapp W In Combinatorial Peptide and Nonpeptide Libraries . Jung G. VCH; Weinheim: 1996: 425
• 10c Du X, Armstrong RW. J. Org. Chem. 1997; 62: 5678
• 10d Gooding OW, Baudert D, Deegan TL, Heisler K, Labadie JW, Newcomb WS, Porco JA. Jr, Eikeren PJ. J. Comb. Chem. 1999; 1: 113
• 11a The specific rotation value for 99% ee (S) of 8aA; [α]_D ²⁵ +37.7 (c 1.0, CHCl₃).
• 11b Mecca T, Superchi S, Giorgio E, Rosini C. Tetrahedron: Asymmetry 2001; 12: 1225
• 12 Clayden J, Kubinski PM, Sammiceli F, Helliwell M, Diorazio L. Tetrahedron 2004; 60: 4387
• 13 Sudo Y, Arai S, Nishida A. Eur. J. Org. Chem. 2006; 752
• 14 Hotta H, Suzuki T, Miyano S. Chem. Lett. 1990; 143
• 15 Cozzi F, Annunziata R, Benaglia M, Cinquini M, Raimondi L, Baldridge KK, Siegel JS. Org. Biomol. Chem. 2003; 1: 157
• 16 Hiney RM, Higham LJ, Müller-Bunz H, Gilheany DG. Angew. Chem. Int. Ed. 2006; 45: 7248