Synthesis of an azabicyclic framework towards (±)-actinophyllic acid

Lewis acid mediated intramolecular Mannich reaction between an azocinone and a 3-formylindole was investigated as part of a study towards the synthesis of actinophyllic acid. The intramolecular Mannich reaction resulted in a single diastereomer of the 1-azabicyclo[4.2.1]nonan-5-one core framework, although single crystal X-ray structure analysis revealed that this had the undesired stereochemistry in comparison with the natural product.     

Current status of automotive fuel cells for sustainable transport

Automotive proton-exchange membrane fuel cells (PEMFCs) have finally reached a state of technological readiness where several major automotive companies are commercially leasing and selling fuel cell electric vehicles, including Toyota, Honda, and Hyundai. These now claim vehicle speed and acceleration, refueling time, driving range, and durability that rival conventional internal combustion engines and in most cases outperform battery electric vehicles. The residual challenges and areas of improvement which remain for PEMFCs are performance at high current density, durability, and cost. These are expected to be resolved over the coming decade while hydrogen infrastructure needs to become widely available. Here, we briefly discuss the status of automotive PEMFCs, misconceptions about the barriers that platinum usage creates, and the remaining hurdles for the technology to become broadly accepted and implemented.     

Representations of Hecke Algebras and Dilations of Semigroup Crossed Products

A family of Hecke C^*-algebras can be realised as crossed productsby semigroups of endomorphisms. It is shown by dilating representationsof the semigroup crossed product that the category of representationsof the Hecke algebra is equivalent to the category of continuousunitary representations of a totally disconnected locally compactgroup.     

The Ramifications of the Centres: Quantised Function Algebras at Roots of Unity

This paper continues the study of quantised function algebrasO[G] of a semisimple group G at an lth root of unity . Thesealgebras were introduced by De Concini and Lyubashenko in 1994,and studied further by De Concini and Procesi and by Gordon,amongst others. Our main purpose here is to increase understandingof the finite-dimensional factor algebras O[G](g), for g G.We determine the representation type and block structure ofthese factors, and (for many g) describe them up to isomorphism.A series of parallel results is obtained for the quantised Borelalgebras and . 2000 Mathematical Subject Classification: 16W35,17B37.     

Intramolecular carbolithiation reactions of chiral alpha-amino-organolithium species

Enantiomerically enriched alpha-amino-organolithium species, in which the lithium atom is attached to a stereogenic carbon centre, have been found to be chemically stable at room temperature in a solvent of very low polarity and undergo intramolecular carbolithiation onto an unactivated alkene. The configurational stability of the chiral organolithium species, bearing a variety of N-alkenyl substituents, was probed by studying the enantiomeric purity of the cyclization products. With N-but-3-enyl-2-lithiopyrrolidine, cyclization to the five-membered ring is more rapid than racemization and a high yield of the pyrrolizidine alkaloid (+)-pseudoheliotridane was obtained with no loss of optical purity. In contrast, with N-pent-4-enyl-2-lithiopyrrolidine, cyclization to the six-membered ring was found to occur with significant loss of optical purity. The cyclization to the six-membered ring was determined to occur with a half-life, t(1/2) approximately 90 min at 23 degrees C. The epimerization of this organolithium species in hexane/Et2O 4:1 was calculated to have a half-life, t(1/2) approximately 30 min at 23 degrees C. Enhanced levels of enantioselectivity for the formation of the indolizidine ring system were obtained using an alkene bearing a terminal phenylthio substituent. With N-[(3-phenylthio)-prop-2-enyl]-2-lithiopyrrolidine, cyclization to the four-membered ring occurs with poor enantioselectivity at low temperature in THF but is highly enantioselective at room temperature in a solvent of very low polarity.     

Improved synthesis of (+/-)-4,12-dihydroxy[2.2]paracyclophane and its enantiomeric resolution by enzymatic methods: planar chiral (R)- and (S)-phanol

(+/-)-4,12-Dihydroxy[2.2]paracyclophane [(+/-)-PHANOL] is readily prepared from [2.2]paracyclophane by an improved synthetic protocol. Enzymatic kinetic resolution of its bis-acetate proceeds with good enantioselection. Separation, hydrolysis, and recrystallization provides both enantiomers of PHANOL in high enantiopurity.     

Fusion and planarization of a quinoidal porphyrin dimer

The crystal structure, near-infrared spectrum and electrochemistry of a quinoidal triply-linked porphyrin dimer are compared with those of its singly-linked precursor; fusing the two porphyrins planarizes the pi-system and reduces the optical HOMO-LUMO gap while increasing the gap between the first oxidation and reduction potentials.     

A Semigroup Crossed Product Arising in Number Theory

Recently Bost and Connes have studied an interesting C*-algebraicHecke algebra arising in number theory. Here it is shown thatthis algebra can be realised as a semigroup crossed product,and be profitably studied using methods developed by the authorsfor analysing Toeplitz algebras. One main result is a characterisationof faithful representations of the Hecke algebra.