Synlett 2005(11): 1743-1745  
DOI: 10.1055/s-2005-871538
LETTER
© Georg Thieme Verlag Stuttgart · New York

Dipolar Cycloaddition and Ring-Closing Metathesis in the Synthesis of the Tetracyclic ABCE Ring System of Manzamine A

Iain Coldham*a, Steven M. Piha, Rémi Rabotb
a Department of Chemistry, University of Sheffield, Brook Hill, Sheffield S3 7HF, UK
Fax: +44(114)2229346; e-Mail: i.coldham@sheffield.ac.uk;
b Department of Chemistry, University of Exeter, Stocker Road, Exeter EX4 4QD, UK
Further Information

Publication History

Received 27 April 2005
Publication Date:
14 June 2005 (online)

Abstract

The tetracyclic ABCE core ring system of the manz­amine alkaloids was prepared with the correct relative stereochemistry by an intramolecular dipolar cycloaddition reaction of an azomethine ylide, followed by a ring-closing metathesis reaction.

10

Spectroscopic data for compound 3: IR (film): νmax = 1720, 1685, 1645 cm-1. 1H NMR (400 MHz, 75 °C, C6D6): δ = 1.12-1.23 (2 H, m), 1.26 (1 H, ddd, J = 13.1, 3.6, 1.6 Hz), 1.35-1.65 (4 H, m), 1.57 (9 H, s), 1.82 (1 H, dd, J = 13.1, 10.6 Hz), 1.85-1.94 (1 H, m), 1.98-2.17 (3 H, m), 2.45 (1 H, ddd, J = 11.8, 5.4, 2.2 Hz), 2.67 (1 H, td, J = 12.2, 6.1 Hz), 2.79 (1 H, d, J = 13.7 Hz), 2.80-2.88 (1 H, m), 2.93 (1 H, ddd, J = 12.9, 9.2, 3.2 Hz), 3.70-3.80 (1 H, m), 3.81-3.95 (1 H, m), 4.28-4.37 (1 H, m), 4.73 (1 H, s), 5.19 (1 H, ddd, J = 12.0, 2.9, 2.0 Hz), 5.44-5.55 (1 H, m). 13C NMR (100 MHz, 75 °C, C6D6): δ = 23.6, 25.3, 27.6, 27.8, 28.3, 32.3, 36.0, 36.1, 40.9, 42.5, 47.7, 50.2, 57.3, 68.9, 79.6, 125.5, 133.3, 154.4, 172.8, 203.9. MS (EI): m/z calcd for C22H32N2O4 [M]: 388.2362; found [M+]: 388.2369. MS: m/z (%) = 388 (100), 332 (60), 244 (76).