David J. Aitken

A practical asymmetric synthesis of homochiral α-arylglycines

Abstract Enantioselective reduction of a series of substituted aryl trichloromethyl ketones with the CBS-catecholborane reagent afforded homochiral aryl trichloromethyl carbinols which have been elaborated to give homochiral α-arylglycines in high e.e.

First asymmetric synthesis of carnosadine

Abstract The first asymmetric synthesis of the naturally-occurring cyclopropane amino acid carnosadine, 1 , has been carried out. Starting from the previously available chiral intermediate 2 , appropriate amine protection and side-chain modifications permitted introduction of the key guanidyl substituent in a short and efficient synthesis to give the title compound in five steps and 45% overall yield.

Synthesis of peptides containing 2,3-methanoaspartic acid

Abstract Simple N -protected di- and tri-peptide methyl esters incorporating (±)-( Z )-2,3-methanoaspartic acid were prepared by oxidation of the corresponding (±)-( Z )-2,3-methanohomoserine-derived peptides.

Synthesis of tamoxifen and 4-hydroxytamoxifen using super-base-metalated propylbenzene

Abstract Propylbenzene is metalated regioseleclively at the α-carbon using the n -BuLi- t -BuOK-TMEDA super-base combination; the resulting carbanion condenses with functionalised benzophenones to provide direct syntheses of tamoxifen and 4-hydroxytamoxifen.

An enantiomerically pure tricyclic isoindoline system by cyclisation of tricarbonyl[η6-(R)-N-cyanomethyl-4-phenyloxazolidine]chromium

Abstract The isolation of isoindoline 4 by oxidative trapping indicates that a tricyclic η5 complex is a contributing form of the anion derived from the title compound 3.

Synthesis of novel cyclopropane nucleoside analogues

Abstract The short syntheses of the (±)-1-cyano-2-(hydroxymethyl)cyclopropyl derivatives and the related (±)-2,3-methanobutyrolactone-2-yl derivatives of uracil, thymine and cytosine are described. The key step is the condensation of an N-cyanomethyl-pyrimidinedione base with epibromohydrin.

A Short Synthesis of trans-Cyclopentane-1,2-Diamine

Abstract A convenient and rapid synthesis of the title compound is described, requiring three steps with no chromatographic purification; the key procedure is a double Curtius rearrangement.

AN ORIGINAL SYNTHESIS OF TRANS-1,2-DIAMINOCYCLOBUTANE

Abstract A new synthesis of trans -1,2-diaminocyclobutane 1 is described, in which the key feature is the novel stereoselective borane-induced reductive ring-expansion reaction of the cyclopropane-iminonitrile 2 to give the cyclobutane 4 . This latter intermediate was also used to prepare a trans -fused rigid analogue of moclobemide.

A binuclear platinum(II) complex using trans-1,2-diaminocyclobutane as a bridging ligand

Abstract Trans-1,2-diaminocyclobutane reacted with K[PtCl3(dmso)] to give the binuclear complex trans-PtCl2(dmso)[μ-trans-H2N (cyclo-C4H6)NH2]trans-PtCl2(dmso). The crystal structure showed an Nue5f8Cue5f8Cue5f8N dihedral angle of 99(2) ° for the bridging diamine ligand.

Tandem reactions of organnometallic reagents with a combined aminonitrile-oxazolidine system

Abstract The reaction of the model combined aminonitrile-oxazolidine system 1 with a variety of Grignard and other organometallic reagents leads to the heterocyclic structures 3-imidazolines 2 and 2-aminomorpholines 3 by tandem addition/substitution reactions. The regioselectivity of the initial attack, and hence the relative proportions of products, varies with the nature of the reagent and the presence of Lewis acidity in the mixture.