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Synlett 2012; 23(19): 2753-2757
DOI: 10.1055/s-0032-1317322
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© Georg Thieme Verlag Stuttgart · New York

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*
Further Information

Publication History

Received: 01 August 2012

Accepted after revision: 05 September 2012

Publication Date:
18 October 2012 (online)

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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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    for this article is available online at http://www.thieme-connect.com/ejournals/toc/synlett.
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  • 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:
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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