Visible-Light-Induced Alkylarylation of Unactivated Alkenes via Radical Addition/Truce-Smiles Rearrangement Cascade.

We disclosed a visible-light-induced alkylarylation reaction of unactivated alkenes via a metal-free radical addition/aryl translocation cascade sequence. Distal olefinic sulfonate was designed as a unique molecular scaffold allowing for a domino process to synthesize valuable alkylarylated alcohols in good yields with excellent diastereoselectivity, featuring mild reaction conditions, broad substrate scope, and excellent functional group tolerance. The mechanism investigation suggests that a visible-light-induced radical chain process dominates the cascade transformation.

Three-component 1,2-dicarbofunctionalization of alkenes involving alkyl radicals.

1,2-Dicarbofunctionalization of alkenes represents an appealing strategy for chemical bond formation in organic synthesis, which could enable the rapid construction of molecular complexity from simple and readily available starting materials by incorporating two functional groups onto a carbon-carbon double bond in one step. In this field, the dicarbofunctionalization of alkenes with different alkyl radicals in a controlled manner represents an elegant and versatile strategy to access structurally diverse functionalized alkanes, which have witnessed significant progress over the last five years. Due to the importance of alkyl radicals in organic synthesis and medicinal chemistry, this review provides a comprehensive perspective on the development of alkyl radical precursors including electrophilic precursors such as alkyl halides, alkyl peroxides, alkyl NHP esters, cycloketone oxime esters, and Katritzky pyridinium salts, and nucleophilic precursors such as alkyl acids, alkyl oxalates, alkylborates, alkylsilicates, and unactivated hydrocarbons, which generate alkyl radicals by photocatalysis or transition metal catalysis to engage in dicarbofunctionalization under oxidative reaction conditions, redox-neutral conditions, or reductive conditions. The mechanisms of these dicarbofunctionalization reactions have also been discussed in detail.

Iodine promoted cascade cycloisomerization of 1-en-6,11-diynes.

An iodine promoted cascade cycloisomerization of 1-en-6,11-diynes is presented for the easy preparation of tetrahydrobenzo[f]isoquinolines. This developed reaction system is identified as having good functional-group applicability and can be scaled up to gram quantities. In this transformation, two new cyclic frameworks and one carbonyl group are formed with four new bonds constructed. Additionally, the resulting iodo-substituted compounds could be further derived through simple elimination reactions.

AgSCF3/Na2S2O8-Promoted Trifluoromethylthiolation/Cyclization of o-Propargyl Arylazides/ o-Alkynyl Benzylazides: Synthesis of SCF3-Substituted Quinolines and Isoquinolines.

A AgSCF3/Na2S2O8-promoted trifluoromethylthiolation/cascade cyclization of o-propargyl arylazides (or o-alkynyl benzylazides) triggered by a carbon-carbon triple bond is reported. This strategy provides the synthesis of valuable SCF3-substituted quinoline and isoquinoline systems via the construction of one C(sp2)-SCF3 bond and one C-N bond within one process.