2,2′-Dihydroxybenzil: A Stereodynamic Probe for Primary Amines Controlled by Steric Strain

Abstract

A rational approach for generating 1,1'-binaphthalene-like axial chirality of a small organic receptor, 2,2'-dihydroxybenzil is presented. The receptor combines with 2 equiv of monodentate primary amines to form a diimine, of which axial chirality is controlled by steric strain with moderate (1.4:1) to good (4.7:1) stereoselectivity. The observed circular dichroism (CD) spectra have been closely simulated by TD-DFT computations and can be used for determining the absolute chirality and enantiomeric excess of primary amines.

On the non-innocence and reactiveversusnon-reactive nature of α-diketones in a set of diruthenium frameworks

“…The observation of such dioxygen driven cleavage activity in 2,2′-pyridil obviously raises the question of the generality of such C-C bond cleavage reactions in related diketocontaining compounds. In this work, the stability/instability of 1,2-bis(2-hydroxyphenyl) ethane-1,2-dione (L) 6 (Scheme 1), a symmetrical bridging ligand composed of a mixed donor (redox active phenoxide, upon deprotonation)acceptor (keto groups) system, and its activity/inactivity towards dioxygen are investigated in a set of ruthenium complexes.…”

Di(1‐naphthyl) methanol ester of carboxylic acids for absolute stereochemical determination

“…Over the past 4 decades, chiroptical spectroscopy, and in particular circular dichroism (CD), has played a pivotal role in the absolute stereochemical determination of organic molecules . Numerous strategies have been devised to address this important issue; nonetheless, it is clear that a unified solution to the problem is not forthcoming.…”

Point-to-Axial Chirality Transmission: A Highly Sensitive Triaryl Chirality Probe for Stereochemical Assignments of Amines

“…Even a cursory review of the available literature precedents led to the conclusion that the efficiency of the chirality sensing of amines is a function of the mode of action of the probe and the method of binding the inductor. − The metalloporphyrin tweezers introduced to a stereochemical analysis by Berova and Nakanishi (Chart a) are considered sensitive probes of the chirality of noncovalently bound species. However, for efficient binding to the probe, an analyte requires the presence of two functional groups in a molecular skeleton.…”