The nonchelate enforced chiral amide enolates derived from 4-7 react with alkyl iodide and protected a-amino epoxide electrophiles to produce the HIV protease inhibitors 10 and 16-19 with high diastereoselectivity.

A new branched carbazole derivative, 1,3,5-tris(2-(9-ethylcarbazyl-3)ethylene)benzene (TECEB), was prepared as a hole-transporting material for organic light-emitting devices (OLEDs). TECEB is comparable to 1,4-bis(1-naphthylphenylamino)biphenyl (NPB) in terms of highest-occupied molecular orbital/lowestunoccupied molecular orbial energy levels, hole-drift mobility, as well as device performance (maximum luminence of about 10 000 cd m -2 and current efficiency of 3.27 cd A -1 ) in a standard hole-transporting layer/tris-(8-hydroxyquinoline)aluminum double-layer device, but is superior to NPB in terms of its higher glass-transition temperature (T g , 130 °C) and ease of synthesis. The latter features suggest that TECEB can be a potential alternative material to NPB especially for high-temperature applications in OLEDs and other organic electronic devices.

Extensive investigations of asymmetric intermolecular cyclopropanation of terminal alkenes with diazoacetates catalyzed by ruthenium porphyrin [Ru(P*)(CO)(EtOH)] (1, H2P = 5,10,15,20-tetrakis[(1S,4R,5R,8S)-1,2,3,4,5,6,7,8-octahydro-1,4:5,8-dimethanoanthracene-9-yl]porphyrin) and the application of catalyst 1 to asymmetric intramolecular cyclopropanation of allylic or homoallylic diazoacetates are described. The intermolecular cyclopropanation of styrene and its derivatives with ethyl diazoacetate afforded the corresponding cyclopropyl esters in up to 98% ee with high trans/cis ratios of up to 36 and extremely high catalyst turnovers of up to 1.1 x 10(4). Examination of the effects of temperature, diazoacetate, solvent, and substituent in the intermolecular cyclopropanation reveals that (i) both enantioselectivity and trans selectivity increase with decreasing temperature, (ii) sterically encumbered diazoacetates N2CHCO2R, such as R = Bu(t), and donor solvents, such as diethyl ether and tetrahydrofuran, are beneficial to the trans selectivity, and (iii) electron-donating para substituents on styrene accelerate the cyclopropanations, with the log(k(X)/k(H)) vs sigma(+) plot for para-substituted styrenes p-X-C6H4CH=CH2 (X = MeO, Me, Cl, CF3) exhibiting good linearity with a small negative rho(+) value of -0.44 +/- 0.09. In the case of intramolecular cyclopropanation, complex 1 promoted the decomposition of a series of allylic diazoacetates to form the cyclopropyl lactones in up to 85% ee, contributing the first efficient metalloporphyrin catalyst for an asymmetric intramolecular cyclopropanation. Both the inter- and intramolecular cyclopropanations were proposed to proceed via a reactive chiral ruthenium carbene intermediate. The enantioselectivities in these processes were rationalized on the basis of the X-ray crystal structures of closely related stable chiral carbene complexes [Ru(P*)(CPh2)] (2) and [Ru(P*)(C(Ph)CO2CH2CH=CH2)] (3) obtained from reactions of complex 1 with N2CPh2 and N2C(Ph)CO2CH2CH=CH2, respectively.

The complex [ A ~~( d p p m ) ~] 2 + [dppm = bis(diphenylphosphino)methane] exhibits a long-lived room temperature photoluminescence in fluid solutions (emission maximum, 565 nm; to, 17.0 ps; excited state of [ A ~~( d p p m ) ~] 2 + undergoes oxidative and reductive quenching with methyl viologen and N,N,N',N'-tetramethyl-p-phenylenediamine, respectively, and can be quenched by organic halides.