Professor Harry Heaney
Emeritus Professor of Organic Chemistry
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%). 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 calixresorcinarenes with both (R)-(+)- and (S)-(-)-a-methylbenzylamine were shown to give products with very high diastereoselectivities. The tetrakis-(1,3-dihydrobenzoxazines) heve been converted into a series of enantiomerically pure C4 symmetric calixresorcinarenes involving the removal of the a-methylbenzyl residue.
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 and the high yield cascade sequence shown in Scheme 2 have been studied.
We have shown that tetrahydrophenanthidinones and other functionalised isoquinolines are available by way of acyliminium ion chemistry. 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. Present studies are aimed particularly towards the synthesis and use of new chiral ligands based on biaryl and calixresorcinarene derivatives that owe their chirality to a chiral axis.
H Heaney, Chem.Revs., 1962, 62, 81-97. The Benzyne and Related Intermediates."
H Heaney and SV Ley, J. Chem. Soc., Perkin Trans. 1, 1973, 499-500. N-Alkylation of Indole and Pyrroles in Dimethyl Sulphoxide."
P Brougham. MS Cooper. DA Cummerson, H Heaney, and N. Thompson, Synthesis, 1987, 1015-1017. Oxidation Reactions Using Magnesium Monoperphthalate: A Comparison with mChloroperoxybenzoic Acid.
M.S. Cooper,H. Heaney, A.J. Newbold, and W.R. Sanderson, Synlett, 1990, 533-535. Oxidation Reactions Using Urea Hydrogen Peroxide - A Safe Alternative to Anhydrous Hydrogen Peroxide.
P.C.B. Page, H. Heaney, and E.P. Sampler, J. Am. Chem. Soc., 1999, 121, 6751-6752. The First Enantioselective Syntheses of Axially Chiral Enantiomerically Pure Calixresorcinarene Derivatives".
H. Heaney and A.J. Newbold, Tetrahedron Lett., 2001, 42, 6607-6609. The Oxidation of aromatic aldehydes by magnesium monoperoxyphthalate and urea-hydrogen peroxide.”
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