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L-glutamate semialdehyde (L-GSA) is an intermediate in biosynthetic pathways including those leading to the carbapenem antibiotics. We describe studies on asymmetric deuteration or hydrogenation of appropriate didehydro-amino acid precursors for the stereoselective synthesis of C-2- and/or C-3-[2H]-labelled L-GSA suitable for use in mechanistic studies.… (More)
The biomimetic synthesis of the crispatene core is reported. The core framework was efficiently generated from an easily synthesized all (E)-tetraene precursor in one step, in good yield.
Phytanoyl-CoA 2-hydroxylase (PAHX), an iron(II) and 2-oxoglutarate-dependent oxygenase, catalyses an essential step in the mammalian metabolism of beta-methylated fatty acids. Phytanoyl-CoA was synthesised and used to develop in vitro assays for PAHX. The product of the reaction was confirmed as 2-hydroxyphytanoyl-CoA by NMR and mass spectrometric analyses.… (More)
[reaction: see text] The solution-phase conformational properties of tetrameric and octameric chains of C-glycosyl alpha-d-lyxofuranose configured tetrahydrofuran amino acids (where the C-2 and C-5 substituents on the tetrahydrofuran ring are trans to each other) were examined using NMR and IR and CD in organic solvents. Studies by NMR and IR demonstrated… (More)
Gamma-turn analogues comprising a modified dipeptide constrained in an eleven-membered ring were prepared by alkene metathesis and analysed by NMR and molecular modelling studies. The results reveal that some of the cyclic analogues form inverse gamma-turns and preferentially adopt conformations determined by the identity of the incorporated amino acid… (More)
[reaction: see text] The preparation of phosphorus-containing trienes featuring two diastereotopic vinyl moieties followed by a diastereoselective ring-closing metathesis is described. This methodology allowed for the synthesis of novel highly functionalized P-stereogenic heterocycles featuring both an exo- and an endocyclic double bond. An investigation… (More)
Observations of an intriguing inverse temperature dependence on reaction rate and a profound induction period in the Soai autocatalytic reaction are reported along with detailed kinetic and NMR investigations of the product alkoxide at low temperatures, leading to the suggestion that the active catalyst is derived in situ from the tetrameric ground state.
Autocatalysis has been extensively studied because it is central to the propagation of living systems. Chemical systems which self-reproduce like living cells would offer insight into principles underlying biology and its emergence from inanimate matter. Protocellular models feature a surfactant boundary, providing compartmentalization in the form of a… (More)