Stereoselective Intramolecular Carbene C–H Insertion Catalyzed by Rhodium(III) Porphyrin Complexes

Abstract

Rhodium(III) porphyrin complexes [Rh(Por)Me] are catalytically active towards stereoselective intramolecular carbene C–H insertions of α-diazoacetamides to give cis-β-lactams or trans-γ-lactams in yields up to 99% with regioselectivities up to 100% and cis/trans ratios up to 83:17 for β-lactams.

Key words

rhodium porphyrin - carbene C–H insertion - stereo­selectivity - intramolecular cyclization - lactams

• References and Notes

• 1 Current address: State Key Laboratory of Chirosciences and Department of Applied Biology and Chemical Technology, The Hong Kong Polytechnic University, Hung Hom, Kowloon, Hong Kong, P. R. of China.

Recent reviews:
• 2a Simonneaux G, Le Maux P, Ferrand Y, Rault-Berthelot J. Coord. Chem. Rev. 2006; 250: 2212
• 2b Lu H, Zhang XP. Chem. Soc. Rev. 2011; 40: 1899
• 2c Che C.-M, Lo VK.-Y, Zhou C.-Y, Huang J.-S. Chem. Soc. Rev. 2011; 40: 1950

Recent reviews:
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• 3b Maas G. Chem. Soc. Rev. 2004; 33: 183
• 3c Doyle MP. Angew. Chem. Int. Ed. 2009; 48: 850
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• 3f Zhu S, Cui X, Zhang XP. Eur. J. Inorg. Chem. 2012; 430
• 4 Recent review: Fantauzzi S, Caselli A, Gallo E. Dalton Trans. 2009; 5434
• 5 Recent review: Che C.-M, Huang J.-S. Chem. Commun. 2009; 3996
• 6a Che C.-M, Huang J.-S, Lee F.-W, Li Y, Lai T.-S, Kwong H.-L, Teng P.-F, Lee W.-S, Lo W.-C, Peng S.-M, Zhou Z.-Y. J. Am. Chem. Soc. 2001; 123: 4119
• 6b Li Y, Huang J.-S, Zhou Z.-Y, Che C.-M. J. Am. Chem. Soc. 2001; 123: 4843
• 6c Li Y, Huang J.-S, Zhou Z.-Y, Che C.-M, You X.-Z. J. Am. Chem. Soc. 2002; 124: 13185
• 6d Li Y, Huang J.-S, Xu G.-B, Zhu N, Zhou Z.-Y, Che C.-M, Wong K.-Y. Chem.–Eur. J. 2004; 10: 3486
• 6e Lai T.-S, Chan F.-Y, So P.-K, Ma D.-L, Wong K.-Y, Che C.-M. Dalton Trans. 2006; 4845
• 7 Thu H.-Y, Tong GS.-M, Huang J.-S, Chan SL.-F, Deng Q.-H, Che C.-M. Angew. Chem. Int. Ed. 2008; 47: 9747
• 8 Wang J.-C, Xu Z.-J, Guo Z, Deng Q.-H, Zhou C.-Y, Wan X.-L, Che C.-M. Chem. Commun. 2012; 48: 4299

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• 10a Choi MK.-W, Yu W.-Y, Che C.-M. Org. Lett. 2005; 7: 1081
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• 12 General Procedure Diazo ester 1 (0.1 mmol) dissolved in toluene (5 mL) was added to a toluene solution (5 mL) containing [Rh(Por)Me] (1 mol%) under an N₂ atmosphere. The reaction mixture was refluxed until 1 was completely consumed. The mixture was concentrated under reduced pressure, and the residue was purified by flash column chromatography using EtOAc–hexane as the eluent to obtain the desired products. Data of β-Lactam 2f Yellow oil. ¹H NMR (300 MHz, CDCl₃): δ = 8.15 (d, J = 5.1 Hz, 2H), 7.43–7.37 (m, 7 H), 5.41 (d, J = 2.8 Hz, 1 H), 4.31 (q, J = 7.1 Hz, 2 H), 3.65 (d, J = 2.8 Hz, 1 H), 1.34 (t, J = 7.1 Hz, 3 H). ¹³C NMR (100 MHz, CDCl₃): δ = 168.2, 161.8, 137.8, 134.6, 129.6, 129.5, 128.6, 126.1, 125.2, 117.1, 64.1, 62.5, 58.3, 14.1. MS (EI): m/z = 340 [M⁺]. HRMS (EI): m/z calcd for C₁₈H₁₆N₂O₅: 340.1059; found: 340.1065. Data of γ-Lactam 4h Colorless oil. ¹H NMR (400 MHz, CDCl₃): δ = 4.28–4.19 (m, 2H), 3.58–3.48 (m, 1H), 3.15–3.11(m, 2H), 3.05–2.91 (m, 1H), 2.79–2.70 (m, 1H), 1.78–1.60 (m, 1H), 1.54–1.45 (m, 2H), 1.31–1.25 (m, 7H), 1.20–1.15 (m, 1H), 0.94–0.85 (m, 9 H). ¹³C NMR (100 MHz, CDCl₃): δ = 169.4, 168.3, 61.5, 55.5, 52.1, 52.0, 48.9, 49.0, 36.3, 33.0, 26.9, 20.4, 16.8, 14.0, 11.2. MS (EI): m/z = 269 [M⁺]. HRMS (EI): m/z calcd for C₁₉H₁₈N₂O₅: 269.1991; found: 269.1992