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Relevant academic research and scientific papers

N-Heterocyclic Carbene-Catalyzed 1,4-Alkylacylation of 1,3-Enynes

The radical relay coupling reaction recently emerged as a powerful synthetic strategy for producing tetrasubstituted allenes. However, bond-forming processes involving the allenyl radical intermediate are mostly limited to those promoted by transition metals. In this report, we describe that a ketyl radical generated from single-electron oxidation of the Breslow intermediate is an excellent coupling partner of allenyl radicals. An organocatalytic 1,4-alkylacylation of 1,3-enynes occurred smoothly in the presence of an aldehyde, a radical precursor, and an N-heterocyclic carbene catalyst. This transformation showed remarkable tolerance to both aromatic and aliphatic aldehydes, enyne substitution, and diversified radical precursors.

Copper-Catalyzed Asymmetric Coupling of Allenyl Radicals with Terminal Alkynes to Access Tetrasubstituted Allenes

In contrast to the wealth of asymmetric transformations for generating central chirality from alkyl radicals, the enantiocontrol over the allenyl radicals for forging axial chirality represents an uncharted domain. The challenge arises from the unique elongated linear configuration of the allenyl radicals that necessitates the stereo-differentiation of remote motifs away from the radical reaction site. We herein describe a copper-catalyzed asymmetric radical 1,4-carboalkynylation of 1,3-enynes via the coupling of allenyl radicals with terminal alkynes, providing diverse synthetically challenging tetrasubstituted chiral allenes. A chiral N,N,P-ligand is crucial for both the reaction initiation and the enantiocontrol over the highly reactive allenyl radicals. The reaction features a broad substrate scope, covering a variety of (hetero)aryl and alkyl alkynes and 1,3-enynes as well as radical precursors with excellent functional group tolerance.

Copper-Catalyzed Enantioselective Radical 1,4-Difunctionalization of 1,3-Enynes

Chiral allenes are important structural motifs frequently found in natural products, pharmaceuticals, and other organic compounds. Asymmetric 1,4-difunctionalization of 1,3-enynes is a promising strategy to construct axial chirality and produce substituted chiral allenes from achiral substrates. However, the previous state of the art in 1,4-difunctionalization of 1,3-enynes focused on the allenyl anion pathway. Because of this, only electrophiles can be introduced into the allene backbones in the second functionalization step, consequently limiting the reaction and allene product types. The development of asymmetric 1,4-difunctionalization of 1,3-enynes via a radical pathway would complement previous methods and support expansion of the toolbox for the synthesis of asymmetric allenes. Herein, we report the first radical enantioselective allene formation via a group transfer pathway in the context of copper-catalyzed radical 1,4-difunctionalization of 1,3-enynes. This method addresses a longstanding unsolved problem in asymmetric radical chemistry, provides an important strategy for stereocontrol with free allenyl radicals, and offers a novel approach to the valuable, but previously inaccessible, chiral allenes. This work should shed light on asymmetric radical reactions and may lead to other enantioselective group transfer reactions.

Gold-Catalyzed Rearrangement of Alkynyl Donor-Acceptor Cyclopropanes to Construct Highly Functionalized Alkylidenecyclopentenes

A gold-catalyzed 1,7-addition-cyclization-elimination cascade sequence performed on a range of alkynyl-substituted donor-acceptor-type cyclopropanes provides facile entry to highly functionalized exo-alkylidenecyclopentenes under very mild conditions. Iso

1,2,3-Triazole: Unique ligand in promoting iron-catalyzed propargyl alcohol dehydration

A 1,2,3-traizole-promoted iron(III)-catalyzed propargyl alcohol dehydration was developed for the synthesis of conjugated enynes. The desired conjugated enynes were prepared in good to excellent yields (up to 95%) with a large substrate scope and excellen