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

Vanessa Kar-Yan Lo; Hung-Yat Thu; Yu-Man Chan; Tsz-Lung Lam; Wing-Yiu Yu; Chi-Ming Che

doi:10.1055/s-0032-1317322

Synlett, Table of Contents

Synlett 2012; 23(19): 2753-2757
DOI: 10.1055/s-0032-1317322

cluster

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

Vanessa Kar-Yan Lo

,

Hung-Yat Thu

,

Yu-Man Chan

,

Tsz-Lung Lam

,

Wing-Yiu Yu

,

Chi-Ming Che*

Abstract

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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

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References

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:

3a Che C.-M, Huang J.-S. Coord. Chem. Rev. 2002; 231: 151
3b Maas G. Chem. Soc. Rev. 2004; 33: 183
3c Doyle MP. Angew. Chem. Int. Ed. 2009; 48: 850
3d Zhou C.-Y, Huang J.-S, Che C.-M. Synlett 2010; 2681
3e Intrieri D, Caselli A, Gallo E. Eur. J. Inorg. Chem. 2011; 5071
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

Selected reviews:

9a Doyle MP, McKervey MA, Ye T. Modern Catalytic Methods for Organic Synthesis with Diazo Compounds. Wiley; New York: 1998
9b Davies HM. L, Beckwith RE. J. Chem. Rev. 2003; 103: 2861 ; and references cited therein
9c Davies HM. L, Manning JR. Nature (London) 2008; 451: 417
9d Doyle MP, Duffy R, Ratnikov M, Zhou L. Chem. Rev. 2010; 110: 704

10a Choi MK.-W, Yu W.-Y, Che C.-M. Org. Lett. 2005; 7: 1081
10b Choi MK.-W, Yu W.-Y, So M.-H, Zhou C.-Y, Deng Q.-H, Che C.-M. Chem.–Asian J. 2008; 3: 1256
10c Lo VK.-Y, Guo Z, Choi MK.-W, Yu W.-Y, Huang J.-S, Che C.-M. J. Am. Chem. Soc. 2012; 134: 7588

11 Wayland BB, Ba S, Sherry AE. J. Am. Chem. Soc. 1991; 113: 5305
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

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