Lithium–Bromide Exchange versus Nucleophilic Addition of Schiff's base: Unprecedented Tandem Cyclisation Pathways

By exploring lithium–bromide exchange reactivity of aromatic Schiff's bases with tert-butyllithium (tBuLi), we have revealed unprecedented competitive intermolecular and intramolecular cascade annulation pathways, leading to valuable compounds, such as iso-indolinones and N-substituted anthracene derivatives. A series of reaction parameters were probed, including solvent, stoichiometry, sterics and organolithium reagent choice, in order to understand the influences that limit such ring-closing pathways. With two viable reactivity options for the organolithium on the imine; namely, nucleophilic addition or lithium–bromide exchange, a surprising competitive nature was observed, where nucleophilic addition dominated, even under cryogenic conditions. Considering the most commonly used solvents for lithium–bromide exchange, tetrahydrofuran (THF) and diethyl ether (Et₂O), contrasting reactivity outcomes were revealed with nucleophilic addition promoted in THF, while Et₂O yielded almost double the conversion of cyclic products than in THF.     

Ultraviolet Absorption Induces Hydrogen‐Atom Transfer in G⋅C Watson–Crick DNA Base Pairs in Solution

Ultrafast deactivation pathways bestow photostability on nucleobases and hence preserve the structural integrity of DNA following absorption of ultraviolet (UV) radiation. One controversial recovery mechanism proposed to account for this photostability involves electron‐driven proton transfer (EDPT) in Watson–Crick base pairs. The first direct observation is reported of the EDPT process after UV excitation of individual guanine–cytosine (G?C) Watson–Crick base pairs by ultrafast time‐resolved UV/visible and mid‐infrared spectroscopy. The formation of an intermediate biradical species (G[?H]?C[+H]) with a lifetime of 2.9 ps was tracked. The majority of these biradicals return to the original G?C Watson–Crick pairs, but up to 10 % of the initially excited molecules instead form a stable photoproduct G*?C* that has undergone double hydrogen‐atom transfer. The observation of these sequential EDPT mechanisms across intermolecular hydrogen bonds confirms an important and long debated pathway for the deactivation of photoexcited base pairs, with possible implications for the UV photochemistry of DNA.     

One-pot synthesis of chiral azetidines from chloroaldehyde and chiral amines

A variety of chiral azetidinepiperidines have been synthesized utilizing an expedient one-pot union of piperidine chloroaldehyde with chiral amines. This two step one-pot procedure provides access to an interesting set of compounds that retain the chiral purity of the starting chiral amine.     

The isomorphism problem for some universal operator algebras

This paper addresses the isomorphism problem for the universal (non-self-adjoint) operator algebras generated by a row contraction subject to homogeneous polynomial relations. We find that two such algebras are isometrically isomorphic if and only if the defining polynomial relations are the same up to a unitary change of variables, and that this happens if and only if the associated subproduct systems are isomorphic. The proof makes use of the complex analytic structure of the character space, together with some recent results on subproduct systems. Restricting attention to commutative operator algebras defined by a radical ideal of relations yields strong resemblances with classical algebraic geometry. These commutative operator algebras turn out to be algebras of analytic functions on algebraic varieties. We prove a projective Nullstellensatz connecting closed ideals and their zero sets. Under some technical assumptions, we find that two such algebras are isomorphic as algebras if and only if they are similar, and we obtain a clear geometrical picture of when this happens. This result is obtained with tools from algebraic geometry, reproducing kernel Hilbert spaces, and some new complex-geometric rigidity results of independent interest. The C^?-envelopes of these algebras are also determined. The Banach-algebraic and the algebraic classification results are shown to hold for the wot-closures of these algebras as well.     

A New Chiral Director for the Highly Diastereoselective Borane Reductionof Steroid-20-ones

 The synthesis of a new chiral boroxazolidine was achieved which was used to control the stereochemistry of the borane reduction of the 20-keto group of steroids. The otherwise hardly accessible 20α-(20S)-alcohol can thus be prepared in a yield of 91%.