1,2-Dicarbofunctionalization of alkenes has emerged as an efficient synthetic strategy for preparing substituted molecules by coupling readily available alkenes with electrophiles and/or nucleophiles Nickel complexes serve as effective catalysts owing to their tendency to undergo facile oxidative addition and slow β-hydride elimination, and their capability to access both two-electron and radical pathways Two-component alkene functionalization reactions have achieved high chemo-, regio-, and stereoselectivities by tethering one of the coupling partners to the alkene substrate Three-component reactions, however, often incorporate directing groups to control the selectivity Only a few examples of directing-group-free difunctionalizations of unactivated alkenes have been reported Therefore, great opportunities exist for the development of three-component difunctionalization reactions with broad substrate scopes and tunable chemo-, regio-, and stereoselectivities

Nickel-Catalyzed Dicarbofunctionalization of Alkenes

Cross-coupling chemistry is widely applied to carbon-carbon bond formation in the synthesis of medicines, agrochemicals, and other functional materials Recently, single-electron–induced variants of this reaction class have proven particularly useful in the formation of C(sp 2 )–C(sp 3 ) linkages, although certain compound classes have remained a challenge Here, we report the use of sulfones to activate the alkyl coupling partner in nickel-catalyzed radical cross-coupling with aryl zinc reagents This method’s tolerance of fluoroalkyl substituents proved particularly advantageous for the streamlined preparation of pharmaceutically oriented fluorinated scaffolds that previously required multiple steps, toxic reagents, and nonmodular retrosynthetic blueprints Five specific sulfone reagents facilitate the rapid assembly of a vast set of compounds, many of which contain challenging fluorination patterns

/pdf/modular-radical-cross-coupling-with-sulfones-enables-access-17j0szqg4u.pdf

Modular radical cross-coupling with sulfones enables access to sp3-rich (fluoro)alkylated scaffolds

The first Suzuki cross-couplings of unactivated tertiary alkyl electrophiles are described. The method employs a readily accessible catalyst (NiBr2·diglyme/4,4′-di-tert-butyl-2,2′-bipyridine, both commercially available) and represents the initial example of the use of a group 10 catalyst to cross-couple unactivated tertiary electrophiles to form C–C bonds. This approach to the synthesis of all-carbon quaternary carbon centers does not suffer from isomerization of the alkyl group, in contrast with the umpolung strategy for this bond construction (cross-coupling of a tertiary alkylmetal with an aryl electrophile). Preliminary mechanistic studies are consistent with the generation of a radical intermediate along the reaction pathway.

Nickel-Catalyzed Carbon–Carbon Bond-Forming Reactions of Unactivated Tertiary Alkyl Halides: Suzuki Arylations

The new millennium has witnessed the rapid development of synthetic organofluorine chemistry all over the world, and chemists in China have made significant contributions in this field. This review aims to provide a brief introduction to China's primary innovations from 2000 to early 2017, covering fluorination, fluoroalkylation, fluoromethylthiolation, fluoroolefination and polyfluoroarylation, as well as synthesis with fluorinated building blocks. Recent advances in the chemistry of difluorocarbene and the chemistry of carbon-fluorine bond activation are also discussed. As a conclusion, the review ends with some personal perspectives on the future development of China's synthetic organofluorine chemistry.

China's flourishing synthetic organofluorine chemistry: innovations in the new millennium

Substantial advances in enantioconvergent C(sp3)-C(sp3) bond formation reactions have been made in recent years through the use of transition-metal-catalyzed cross-coupling reactions of racemic secondary alkyl electrophiles with organometallic reagents. Herein, we report a general process for the asymmetric construction of alkyl-alkyl bonds adjacent to heteroatoms, namely, a nickel-catalyzed enantioconvergent reductive hydroalkylation of olefins with α-heteroatom phosphorus or sulfur alkyl electrophiles. Including the use of readily available olefins, this reaction has considerable advantages, such as mild reaction conditions, a broad substrate scope, and good functional group compatibility, making it a desirable alternative to traditional electrophile-nucleophile cross-coupling reactions.

Nickel-Catalyzed Enantioconvergent Reductive Hydroalkylation of Olefins with α-Heteroatom Phosphorus or Sulfur Alkyl Electrophiles.

Aryl boronic acids can be monofluoromethylated under nickel catalysis. The utility of this method is demonstrated by the monofluoromethylation of a borylated and acyl-protected derivative of the statin drug ezetimibe. Mechanistic investigations indicate that a fluoromethyl radical is involved in the Ni(I)/Ni(III) catalytic cycle.

Nickel-catalyzed monofluoromethylation of aryl boronic acids.

A novel palladium-catalyzed C-7 selective CH carbonylation of indolines with carbon monoxide for an expedient synthesis of pyrroloquinazolinediones, a structural motif with great potential in biologically active compounds, has been developed. Oxidation of the pyrroloquinazolinedione with 2,3-dichloro-5,6-dicyano-p-benzoquinone (DDQ) could easily afford the corresponding indole-based derivative in excellent yield.

Palladium-Catalyzed C-7 Selective CH Carbonylation of Indolines for Expedient Synthesis of Pyrroloquinazolinediones

Palladium‐Catalyzed C‐7 Selective C—H Carbonylation of Indolines for Expedient Synthesis of Pyrroloquinazolinediones.

The reaction of phenylsulfonyl or ester activated monofluoro monohalomethanes with arylboronic acids is achieved in the presence of a nickel catalyst to yield the corresponding fluoromethylaryl derivatives.

Nickel-Catalyzed Monofluoromethylation of Aryl Boronic Acids.

Terminal C(sp3)H alkylation of internal alkenes via Ni/H-catalyzed isomerization

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