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Fluorine-containing moieties show significant effects in improving the properties of functional molecules. Here the authors show diazaphospholene-catalyzed hydrodefluorination of trifluoromethylalkenes to chemoselectively construct gem-difluoroalkenes and terminal monofluoroalkenes by simple adjustment of the reactant stoichiometry.

Summary: Functionalization of α-C–H bonds of tertiary amines to build various α-C–X bonds has become a mainstream in synthetic chemistry nowadays. However, due to lack of fundamental knowledge on α-C–H bond strength as an energetic guideline, rational exploration of new synthetic methodologies remains a far-reaching anticipation. Herein, we report a unique hydricity-based approach to establish the first integrated energetic scale covering both the homolytic and heterolytic energies of α-C–H bonds for 45 representative tertiary amines and their radical cations. As showcased from the studies on tetrahydroisoquinolines (THIQs) by virtue of their thermodynamic criteria, the feasibility and mechanisms of THIQ oxidation were deduced, which, indeed, were found to correspond well with experimental observations. This integrated scale provides a good example to relate bond energetics with mechanisms and thermodynamic reactivity of amine α-C–H functionalization and hence, may be referenced for analyzing similar structure-property problems for various substrates. : Organic Chemistry; Organic Synthesis; Physical Organic Chemistry Subject Areas: Organic Chemistry, Organic Synthesis, Physical Organic Chemistry

This article addresses the problem of adaptive finite-time neural tracking control for nonstrict-feedback nonlinear systems via dynamic surface (DS) technique. First, a new quasi-fast finite-time practical stability (QFPS) criterion is proposed for a class of general nonlinear systems. Then, the presented QFPS criterion is applied to design the desired adaptive finite-time neural tracking controller for a class of nonstrict-feedback nonlinear systems. The presented design scheme for the nonstrict-feedback nonlinear system has the following two features: 1) the “explosion of complexity” issue of the backstepping design is addressed by utilizing the DS technique and 2) the structural feature of Gaussian functions is applied to solve the design difficulties caused by the nonstrict-feedback form. It is proved that the designed controller for the nonstrict-feedback nonlinear system can make the resulting closed-loop system stabilizable in a quasi-fast finite time and the tracking error converges to a sufficiently small neighborhood of the origin. Finally, the simulation results are given to show the validity and practicability of the proposed design scheme. [ABSTRACT FROM AUTHOR]

The kinetics and stereochemistry of the reactions of iminium ions derived from cinnamaldehydes and MacMillan's imidazolidinones with diphenyldiazomethane and aryldiazomethanes were investigated experimentally and with DFT calculations. The reactions of diphenyldiazomethane with iminium ions derived from MacMillan's second‐generation catalysts gave 3‐aryl‐2,2‐diphenylcyclopropanecarbaldehydes with yields >90 % and enantiomeric ratios of ≥90:10. Predominantly 2:1 products were obtained from the corresponding reactions with monoaryldiazomethanes. The measured rate constants are in good agreement with the rate constants derived from the one‐center nucleophilicity parameters N and sN of diazomethanes and the one‐center electrophilicity parameters E of iminium ions as well as with quantum chemically calculated activation energies. [ABSTRACT FROM AUTHOR]

A metal-free, visible-light-induced photocatalytic procedure for decarboxylative alkynylation of carboxylic acids was reported. With 9,10-dicyanoanthracene as the photoredox catalyst, the reaction covered a broad scope of α-amino acids, α-oxo acids, and α-keto acids with blue LED irradiation at room temperature under an atmosphere of argon, delivering alkynyl products in moderate to excellent yields. Natural sun light also promoted this alkynylation strategy. This work represents the first example of an organophotocatalytic method for decarboxylative alkynylation of carboxylic acids. [ABSTRACT FROM AUTHOR]