Synthetic Studies Concerning the Crinine Alkaloid Haemultine

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doi:10.1071/CH12473

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Synthetic Studies Concerning the Crinine Alkaloid Haemultine

Nadia (Yuqian) Gao ^A, Xinghua Ma ^A, Laurent Petit ^A, Brett D. Schwartz ^A, Martin G. Banwell ^A ^B, Anthony C. Willis ^A, Ian A. Cade ^A and A. David Rae ^A

^A Research School of Chemistry, Institute of Advanced Studies, The Australian National University, Canberra, ACT 0200, Australia.
^B Corresponding author. Email: mgb@rsc.anu.edu.au

Australian Journal of Chemistry 66(1) 30-39 http://dx.doi.org/10.1071/CH12473
Submitted: 15 October 2012 Accepted: 9 November 2012 Published: 14 January 2013





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Abstract

The racemic form, (±)-1, of the structure originally assigned to the crinine alkaloid haemultine has been prepared for the first time. A key step involved the conversion of compound (±)-4 into the isomeric cis-C3a-arylhexahydroindole (±)-3 using a Pd⁰-catalysed intramolecular Alder-ene reaction. The amino-alcohol (±)-2 derived from the latter compound reacted with paraformaldehyde in the presence of trifluoroacetic acid to give, via a Pictet–Spengler reaction, the target (±)-1. The diastereoisomeric Mosher esters 15 and 16 obtained by coupling the racemate (±)-1 with the R-form, 14, of the Mosher acid could be separated chromatographically and then reductively cleaved to give the enantiomerically pure compounds (+)-1 and (–)-1, respectively. The physical and spectroscopic data derived from the former enantiomer are consistent with the proposition that the title natural product is, in fact, a mixture of (+)-1 and its Δ^2,3-double bond isomer.

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