Catalytic Dehydrogenation of Amine-Boranes using Geminal Phosphino-Boranes

The reaction of the intramolecular frustrated Lewis pair (FLP) tBu₂PCH₂BPh₂ with the amine-boranes NH₃ · BH₃ and Me₂NH · BH₃ leads to the formation of the corresponding FLP-H₂ adducts as well as novel five-membered heterocycles that result from capturing the in situ formed amino-borane by a second equivalent of FLP. The sterically more demanding tBu₂PCH₂BMes₂ does not form such a five-membered heterocycle when reacted with Me₂NH · BH₃ and its H₂ adduct liberates dihydrogen at elevated temperatures, promoting the metal-free catalytic dehydrogenation of amine-boranes.     

A Structurally Robust Chiral Borate Ion: Molecular Design,Synthesis, and Asymmetric Catalysis

Catalysis by chiral weakly-coordinating anions (WCAs) remains underdeveloped due to the lack of a molecular design strategy for exploiting their characteristics, such as the non-nucleophilic nature. Here, we report the development of a chiral borate ion comprising an O,N,N,O-tetradentate backbone, which ensures hitherto unattainable structural robustness. Upon pairing with a proton, the hydrogen borate acts as an effective catalyst for the asymmetric Prins-type cyclization of vinyl ethers, providing access to structurally and stereochemically defined dihydropyrans. The key to selectivity control is the distinct ability of the borate ion to discriminate the prochiral faces of the acyclic oxonium ion intermediate and dictate the regiochemical outcome. We anticipate that this study paves the way for exploring the untapped potential of WCA catalysis for selective chemical synthesis.     

Asymmetric Ring-Opening of Cyclohexene Oxide with Mercaptan (Thiophenols) Catalyzed by Chiral Schiff Base/Ti(OPr- i ) 4 or (−)-(S)-Binaphthol/Ti(OPr- i ) 4

New chiral Schiff base ligands 1-4 were synthesized starting from (+)-camphor and (+)-1-(4-nitrophenyl)-2-amino-1,3-propanediol, and their application in asymmetric ring-opening of cyclohexene oxide using mercaptan (thiophenols) as nucleophiles was investigated. The aymmetric ring-opening of cylohexene oxide catalyzed respectively by chiral Schiff bases 1-4 /Ti(OPr- i ) 4 and ( m )-(S)-1,1'-binaphthalene-2,2'-diol 5 /Ti(OPr- i ) 4 complex afforded the corresponding chiral g -hydroxysulfides 6-10 in lower to good yield with lower to moderate ee values. Moreover, the using of ( m )-(S)-1,1'-binaphthalene-2,2'-diol as ligand led to better chiral induction effect.     

Higher moments of certain <Emphasis Type="Italic">L</Emphasis>-functions on the critical line

We study the sixth-power moments of certain L-functions belonging to a sub-class of the Selberg’s class on the critical line and, using this, we conclude an upper bound for the fourth-power moments of certain L-functions related to GL ₃ on the critical line. This is an analogue of the upper bound for the twelfth-power moment of the Riemann zeta-function on the critical line. Published in Lietuvos Matematikos Rinkinys, Vol. 47, No. 3, pp. 341–380, July–September, 2007.     

Noetherian types of homogeneous compacta and dyadic compacta

The Noetherian type of a space is the least κ such that it has a base that is κ-like with respect to reverse inclusion. Just as all known homogeneous compacta have cellularity at most c, they satisfy similar upper bounds in terms of Noetherian type and related cardinal functions. We prove these and many other results about these cardinal functions. For example, every homogeneous dyadic compactum has Noetherian type ω. Assuming GCH, every point in a homogeneous compactum X has a local base that is c(X)-like with respect to containment. If every point in a compactum has a well-quasiordered local base, then some point has a countable local π-base.     

Characterization of the Zwitterionic Intermediate in 1,1-Carboboration of Alkynes

The reaction of a Lewis acidic borane with an alkyne is a key step in a diverse range of main group transformations. Alkyne 1,1-carboboration, the Wrackmeyer reaction, is an archetypal transformation of this kind. 1,1-Carboboration has been proposed to proceed through a zwitterionic intermediate. We report the isolation and spectroscopic, structural and computational characterization of the zwitterionic intermediates generated by reaction of B(C₆F₅)₃ with alkynes. The stepwise reactivity of the zwitterion provides new mechanistic insight for 1,1-carboboration and wider B(C₆F₅)₃ catalysis. Making use of intramolecular stabilization by a ferrocene substituent, we have characterized the zwitterionic intermediate in the solid state and diverted reactivity towards alkyne cyclotrimerization.     

Finite-reductive dual pairs in G2

This paper classifies dual pairs (F,G^′) in complex G₂ where F is finite and G^′ is infinite complex reductive.