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We have disclosed an alkenes dicarbofunctionalization method to introduce alkyl and electron‐rich aryl across the C=C bond of styrenes under copper catalyst and oxidative conditions, leading to construct C(sp3)‐C(sp2)/C(sp3)‐C(sp3) bonds via dual C−H functionalization. This method realizes the synthesis of 1,1‐diarylalkanes, which are very important skeleton in natural products and drug molecules, through the grafting of electron‐rich aromatics, including indoles, pyrroles, trisubstituted aromatic. [ABSTRACT FROM AUTHOR]

Owing to their easy availability and cheapness, simple alkyl chlorides are good raw materials for introducing complex polychlorinated groups. Polychlorinated hydrocarbons units, such as di‐ or trichloromethyl groups, not only widely found in pesticide and bioactive molecule, but also can be as a precursor to converted into different functional groups such as −COOH, −CHO and −CO. The direct polychloroalkylation reaction by using simple alkyl chlrides has been considered to be an important tool for synthesizing complex polychlorinated compounds. This review summarizes recent developments, especially free radical strategies, in the polychloroalkylation of different substrates (such as 2‐acylpyridines, benzyl tertiary amines, alkenes, imine and 1,n‐enynes). We hope that this review provides a new perspective on this field and also provides a reference to develop environmentally friendly and sustainable methods. [ABSTRACT FROM AUTHOR]

A new, radical-mediated, divergent bicyclization of 1,n-enynes by α-C( sp3)-H oxidative functionalization of alkyl nitriles is described using the Sc(OTf)3 and Ag2O system. The reaction allows the selective functionalization of one or two C( sp3)−H bonds α to the nitrile group by both oxidants and the substitution effect co-controlled the divergent bicyclization reactions, and offers a step- and atom-economical access to diverse polycycles with broad substrate scope and high selectivity. [ABSTRACT FROM AUTHOR]

A new copper-mediated synthesis of α-sulfonylethanone oximes from styrenes, sodium arylsulfinates and tert-butyl nitrite ( t-BuONO; TBN) is presented. This intermolecular three-component method enables the one-step formation of CN and CS bonds under mild conditions, and represents a new, straightforward approach to α-sulfonylethanone oximes. [ABSTRACT FROM AUTHOR]

A new visible light-initiated 1,5-hydride radical shift strategy has been developed to enable the one-step functionalization of both a C( sp3)Br bond and a C( sp3)H bond adjacent to the same carbon atom. This visible light photoredox catalysis offers a mild and straightforward access to diverse five-membered carbocyclic ring-fused polycyclic hydrocarbons with high turnover numbers (TONs; up to 4.93×103) and broad substrate scope. [ABSTRACT FROM AUTHOR]

A metal-free radical-mediated [4+2] annulation of internal arylalkynes with tert-butyl nitrite (t-BuONO) is presented for the synthesis of benzo[e][1,2]oxazin-4-ones through the addition of t-BuONO across the CŽ≡C triple bond, hydration, isomerization and aromatic C(sp2)--H oxidation cascades. The 18O-labeling experiment shows that two oxygen atoms in the product system are from water. [ABSTRACT FROM AUTHOR]

A new method for the nitrative spirocyclization of alkynes is described. This method involves the oxidative difunctionalization of alkynes initiated by a radical attack pathway using t-BuONO ( tert-butyl nitrite) combined with water as the nitro source and TEMPO [(2,2,6,6-tetramethyl-piperidin-1-yl)oxyl] as the initiator, and it represents a new example of oxidative alkyne difunctionalization via the formation of CN/CC bonds for the assembly of nitroalkene unit-containing spirocycles. [ABSTRACT FROM AUTHOR]

A novel copper-catalyzed oxidative alkylation of α-amino carbonyl compounds with ethers has been established for the selective synthesis of α-etherized α-amino carbonyl compounds. This oxidative alkylation is achieved by dual C( sp3)H bond oxidative cross-coupling, and its scope is expanded to α-amino ketones, α-amino esters and α-amino amides. [ABSTRACT FROM AUTHOR]