Decarboxylative alkenylation

Abstract

Olefin chemistry, through pericyclic reactions, polymerizations, oxidations, or reductions, plays an essential role in the foundation of how organic matter is manipulated.1 Despite its importance, olefin synthesis still largely relies upon chemistry invented more than three decades ago, with metathesis2 being the most recent addition. Here we describe a simple method to access olefins with any substitution pattern or geometry from one of the most ubiquitous and variegated building blocks of chemistry: alkyl carboxylic acids. The same activating principles used in amide-bond synthesis can thus be employed, under Ni- or Fe-based catalysis, to extract CO2 from a carboxylic acid and economically replace it with an organozinc-derived olefin on mole scale. Over sixty olefins across a range of substrate classes are prepared, and the ability to simplify retrosynthetic analysis is exemplified with the preparation of sixteen different natural products across a range of ten different families.

Synthesis of E- and Z-trisubstituted alkenes by catalytic cross-metathesis

“…Mo chloride complexes are ineffective in promoting reactions that afford alkenyl halides, as decomposition of the purported chloro- or bromo-substituted metallacyclobutanes is probably facile 37 . The present approach complements a recent study regarding stereoselective synthesis of trisubstituted alkenes starting from carboxylic acids and involving alkenylzinc reagents, which are often derived from alkenyl halide precursors 38 .…”

Iron‐Catalyzed C−O Bond Activation: Opportunity for Sustainable Catalysis

“…[64] Conceptually, ar elated method, which exploits carboxylic acid derivatives as couplingp artners for iron-catalyzedC ÀC bond formation, was reported by Bao and co-workers (Scheme 33). [64] Conceptually, ar elated method, which exploits carboxylic acid derivatives as couplingp artners for iron-catalyzedC ÀC bond formation, was reported by Bao and co-workers (Scheme 33).…”

“…Iron-catalyzed decarboxylativec ross-coupling of esters alkenyl zinc reagents by Baran et al [64] ChemSusChem 2017, 10,3964 -3981 www.chemsuschem.org and excellent functionalg roup tolerance (Br,C l, OH, benzyl, allyl, terminal alkynyl). Iron-catalyzed decarboxylativec ross-coupling of esters alkenyl zinc reagents by Baran et al [64] ChemSusChem 2017, 10,3964 -3981 www.chemsuschem.org and excellent functionalg roup tolerance (Br,C l, OH, benzyl, allyl, terminal alkynyl).…”

Deaminative Strategy for the Visible‐Light‐Mediated Generation of Alkyl Radicals

“…[1] Furthermore, methodst hatc an use naturallya bundanta nd inexpensivef eedstockst og enerate alkylr adicalsare of high interest in modern synthetico rganic chemistry. [5] Primary amines are another feedstock of similar natural abundance to carboxylic acids, [6] and so naturally,anumber of methods have been developed to exploit them as synthetic intermediates in two-electron processes. [5] Primary amines are another feedstock of similar natural abundance to carboxylic acids, [6] and so naturally,anumber of methods have been developed to exploit them as synthetic intermediates in two-electron processes.…”