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Synlett 2007(11): 1663-1666  
DOI: 10.1055/s-2007-982573
LETTER
© Georg Thieme Verlag Stuttgart · New York

Ring-Rearrangement Metathesis of Substituted 2-Aminonorbornenes

Adam E. Nadany, John E. Mckendrick*
Department of Chemistry, University of Reading, Whiteknights, Reading, RG6 6AD, UK
Fax: +44(118)3786331; e-Mail: j.e.mckendrick@reading.ac.uk;
Further Information

Publication History

Received 3 April 2007
Publication Date:
25 June 2007 (online)

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Abstract

In this report we describe the ring-rearrangement meta­thesis of 2-aminonorbornene derivatives. An efficient ruthenium-catalysed metathesis reaction occurs with a wide range of pendent alkenes and alkynes to generate bicyclic amines and amides.

Key words

metathesis - Diels-Alder reaction - piperidine alkaloids

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Spectroscopic Data for 5a
1H NMR (400 MHz, CDCl3, 70 °C): δ = 1.35-1.38 (m, 1 H, CH2CHN), 1.35-1.38 (m, 1 H, CH2CHCHN), 2.12-2.33 (m, 1 H, CH2CHN), 2.12-2.33 (m, 1 H, CH2CHCHN), 2.12-2.33 (m, 1 H, CHCH2CHN), 2.90-2.94 (m, 1 H, CHCHN), 3.69 (dt, 1 H, CHN, J = 10.5, 6.5 Hz), 4.06 (d, 1 H, CH2Ph, J = 15.0 Hz), 4.90-5.03 (m, 2 H, CH=CH2), 5.29 (d, 1 H, CH2Ph, J = 15.0 Hz), 5.71 (ddd, 1 H, CH=CH2, J = 17.0, 13.0, 7.0 Hz), 5.87 (dd, 1 H, HC=CH, J = 10.0, 2.5 Hz), 6.24 (dd, 1 H, HC=CH, J = 10.0, 3.0 Hz), 7.25-7.33 (m, 5 H, 5 × ArH). 13C NMR (100 MHz, CDCl3, 70 °C): δ = 36.6 (CHCHN), 38.6 (CH2CHCHN), 39.0 (CH2CHN), 40.1 (CHCH2CHN), 48.5 (CH2Ph), 58.7 (CHN), 114.5 (CH=CH2), 122.0 (HC=CH), 127.8 (1 × ArH), 128.4 (2 × ArH), 129.0 (2 × ArH), 138.0 (1 × Ar), 141.2 (CH=CH2), 143.4 (HC=CH), 162.7 (C=O). IR (thin film): 1610 (C=C), 1667 (C=O), 2955 (sat. C-H) cm-1. MS: m/z calcd: 254.1546 [MH+]; found: 254.1546.

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General Procedure for Olefin Metathesis, Synthesis of 8c
A flask was charged with toluenesulfonyl amine 7c (91 mg, 0.3 mmol) and CH2Cl2 (90 mL). Ethene gas was bubbled through the solution for 20 s. Then, Grubbs I catalyst (25 mg, 0.03 mmol) was added to the reaction. A balloon filled with ethene gas was placed over the flask and the reaction was allowed to stir at r.t. overnight. The reaction mixture was then concentrated and subjected to column chromatography eluting PE-Et2O (19:1 to 4:1) to furnish 8c as a colourless oil (89 mg), 99% yield. 1H NMR (400 MHz, CDCl3): δ = 1.11 (ddd, 1 H, CH2CHN, J = 13.5, 8.0, 4.0 Hz), 1.33 (dd, 1 H, H2CHCHC=CH, J = 14.5, 7.5 Hz), 1.66 (dt, 1 H, H2CHCHC=CH, J = 12.0, 6.5 Hz), 2.13 (td, 1 H, CH2CHN, J = 16.0, 13.5 Hz), 2.41 (s, 3 H, CH3), 2.41-2.43 (m, 1 H, HCHC=CH), 2.60-2.65 (br m, 1 H, HCHC=CH2), 3.45-3.50 (m, 1 H, CH2N), 4.06-4.10 (m, 1 H, CH2N), 4.37 (dt, CHN, 1 H, J = 12.0, 7.0 Hz), 4.83-4.94 (m, 2 H, HC=CH2), 5.51-5.61 (m, 2 H, HC=CH), 5.64 (ddd, 1 H, HC=CH2, J = 17.5, 10.0, 7.5 Hz), 7.30 (app. d, 2 H, ArH, J = 8.5 Hz), 7.70 (app. d, 2 H, ArH, J = 7.5 Hz). 13C NMR (100 MHz, CDCl3): δ = 21.5 (CH3), 32.0 (H2CHCHC=CH), 35.4 (HCHC=CH2), 35.8 (CH2CHN), 39.4 (CH2N), 39.7 (HCHC=CH), 55.6 (CHN), 113.1 (HC=CH2), 120.0 (HC=CH), 127.2 (2 × ArCH), 129.6 (2 × ArCH), 130.8 (HC=CH), 136.8 (1 × ArC), 142.4 (HC=CH2), 143.2 (1 × Ar). IR (thin film): 1162, 1384 (SO2), 2975 (sat. C-H) cm-1. MS: m/z calcd for 303.1290 [M+]; found: 303.1293.