Ring-Rearrangement Metathesis of Substituted 2-Aminonorbornenes

Adam E. Nadany; John E. Mckendrick

doi:10.1055/s-2007-982573

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Synlett 2007(11): 1663-1666
DOI: 10.1055/s-2007-982573

LETTER

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;

Weitere Informationen

Publikationsverlauf

Received 3 April 2007
Publikationsdatum:
25. Juni 2007 (online)

Abstract
Volltext
Referenzen

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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

References and Notes

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15

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.

18

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.