People in the Department

Professor Harry Heaney

Emeritus Professor of Organic Chemistry
PhD Manchester, DSc Keele
Telephone: 44 + 1509 222555
e-mail: H.Heaney@lboro.ac.uk

Ongoing areas of research are centred on nitrogen heterocyclic chemistry and involve a range of reaction types, including new ligands for use in enantioselective reactions. 8-Phenylmenthyl-a-hydroxyacetates derived from indoles and pyrroles have been used to generate different diastereomers in Friedel-Crafts alkylation reactions. The conversion of a number of pyrrole and indole derivatives into the appropriately related 2- or 3-substituted 8-phenylmenthyl-a-hydroxyacetates and their conversion into diarylacetetates were mostly obtained with high diastereomeric excesses (>96%).¹ The Friedel-Crafts reactions, initiated by electrophiles such as TMS triflate and scandium triflate, are illustrated in Scheme 1. The Mannich reactions of a number of calix[4]resorcinarenes with both (R)-(+)- and (S)-(-)-a-methylbenzylamine were shown to give products with very high diastereoselectivities.² The tetrakis-(1,3-dihydrobenzoxazines) heve been converted into a series of enantiomerically pure C4 symmetric calix[4]resorcinarenes involving the removal of the a-methylbenzyl residue.³

Studies of the intramolecular reactions of acyliminium ions have been facilitated by access to various nmr experiments that are available. The synthesis of the neuvamine skeleton ⁴ and the high yield cascade sequence⁵ shown in Scheme 2 have been studied.

We have shown that tetrahydrophenanthidinones and other functionalised isoquinolines are available by way of acyliminium ion chemistry.⁶ The oxidation of a number of homophthalimide derivatives by dioxygen in an alkaline medium provides a new route to phthalide-amides, precursors to analogues of biologically active phthalide isoquinoline alkaloids, exemplified in Scheme 3.⁷ Present studies are aimed particularly towards the synthesis and use of new chiral ligands based on biaryl and calix[4]resorcinarene derivatives that owe their chirality to a chiral axis.

Selected References:

P.C.B. Page, H. Heaney, G.A. Rassias, S. Regnier, E.P. Sampler, and S. Talib, Synlett, 2000, 104-106. "The Reductive Cleavage of Cyclic Aminol Ethers to N,N-Dialkylamino- derivatives: Modifications to the Eschweiler-Clarke Procedure".

H.Heaney and M.O. Taha, Tetrahedron Lett., 2000, 41, 1993-1996. "N-Acyliminium ion cyclisation versus rearrangement. The synthesis of 13,13-dimethylberberines and 3,4-dimethyliosquinolin-1-ones".

G. Arnott, P.C.B. Page, H. Heaney, R. Hunter, E.P. Sampler, Synlett, 2001, 412-414. "Chiral, Non-racemic, Distally-bridged Resorcin[4]arenes as Models for Use in Asymmetric Processes"

P.C.B. Page, H. Heaney, and E.P. Sampler, J. Am. Chem. Soc., 1999, 121, 6751.

H. Heaney, M.T. Simcox, A.M..Z. Slawin, and R.G. Giles, Synlett, 1998, 640.

H. Heaney, M.O. Taha, and A.M..Z. Slawin, Tetrahedron Lett., 1997, 38, 3051.

M.T. ElGihani, H. Heaney, and K.F. Shuhaibar, Synlett, 1996, 871.

H. Heaney and M.O. Taha, Synlett, 1996, 820.

D.S. Brown, M.J. Earle, M.T. ElGihani, and H. Heaney, Synlett, 1995, 269;

M.T. ElGihani, H. Heaney, and A.M.Z. Slawin, Tetrahedron Lett., 1995, 36, 4905.

H. Heaney and K.F. Shuhaibar, Synlett, 1995, 47.