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Comprehensive Summary: Herein, we report nickel‐catalyzed cross‐coupling of gem‐difluorinated cyclopropanes with boronic acids, providing the corresponding arylated 2‐fluoroallylic scaffolds. This approach used commercially available phosphine ligand Xantphos to obtain monofluorinated alkenes with high regioselectivity and Z‐stereoselectivity. Mechanistic studies proposed a Ni(II)‐fluoroallyl pathway and excluded the radical pathway. Meanwhile, DFT study of the reductive elimination clarified the origin of the high linear selectivity. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: A highly enantioselective gold‐catalyzed intermolecular [3 + 2] cycloaddition of N‐allenamides with nitrones was realized by the application of Ming‐Phos M6 as a chiral ligand. Both enantiomers of the cycloadducts with opposite configuration could be obtained in high yields with high regio‐ and enantioselectivity by the employment of either diastereomer of the chiral ligand. The acidic N—H bond (hydrogen bonding) of sulfinamide moiety of Ming‐Phos and pentaflurophenyl substituent (fluorine effect) may play important roles in enhancement of enantioselectivity, that is, Ming‐Phos is a multifunctional ligand in this transformation. [ABSTRACT FROM AUTHOR]

Comprehensive Summary: Atropisomeric anilides are one of important C—N axially chiral compounds. Compared with the N‐terminal functionalization to prepare such compounds, C‐terminal functionalization strategies have been rarely reported. We describe herein an efficient synthesis of axially chiral anilides enabled by Pd‐catalyzed desymmetric Sonogashira cross‐coupling reactions with the use of a newly identified Ming‐Phos. Moderate to high yields with high enantioselectivities (up to 98% ee) were obtained. [ABSTRACT FROM AUTHOR]

Main observation and conclusion: A highly enantioselective palladium‐catalyzed intermolecular tandem Heck/Cacchi reaction of unactivated alkenes with ortho‐ethynylanilines was developed, which provides a powerful route to access a broad range of enantioenriched 2,3‐dihydrobenzofuran‐ or indoline‐substituted indoles bearing all‐carbon quaternary stereocenter of interest in pharmaceutical research. Its salient features include inherent atom‐ and step‐economy, high functional group tolerance, mild conditions, broad structural diversity together with excellent enantioselectivities. [ABSTRACT FROM AUTHOR]

Summary of main observation and conclusion: A visible light driven Cu(I)‐catalyzed intermolecular oxyamination of electron‐deficient olefins has been achieved by using O‐benzoylhydroxylamines as donors both for amine and oxygen. The transformation properties afford mild conditions and a wide substrate scope, providing access to ester derivatives of β‐amino alcohols with good yields and high regioselectivity. [ABSTRACT FROM AUTHOR]

Summary of main observation and conclusion: A gold(I)‐catalyzed asymmetric intermolecular tandem [3+3]‐cyclization reaction of 2‐(1‐alkynyl)‐2‐ alken‐1‐ones with nitrones has been developed by using Ming‐Phos as a chiral ligand. This method enables access to the stereodivergent synthesis of highly substituted furo[3,4‐d][1,2]oxazines in excellent efficiency and stereoselectivity (up to 99% yield, 99% ee, >20 : 1 dr). [ABSTRACT FROM AUTHOR]

Abstract: A gold(I)‐catalyzed highly diastereo‐ and enantioselective intermolecular cycloaddition of oxime ethers with nitrones under mild conditions was developed, which provides an facile access to optically pure highly substituted pyrrolo[3,4‐d][1,2]oxazines. The salient features of this reaction include general substrate scope, high efficiency, high enantioselectivity, readily available starting materials, and the use of commercially available ligand. [ABSTRACT FROM AUTHOR]

Abstract: Reported herein is an example of highly regio‐, diastereo‐ and enantioselective Cu(I)‐catalyzed intermolecular [3+2] cycloaddition reaction of α‐substituted iminoesters with α‐trifluoromethyl α,β‐unsaturated esters. This novel strategy provided a facile access to pyrrolidines with two skipped (aza)quaternary stereocenters including a CF3 all‐carbon quaternary stereocenter. A broad substrate scope was observed and high yields (up to 94%) with excellent diastereoselectivity (up to >20 : 1 d.r.) and enantioselectivity (up to 98% ee) were obtained. [ABSTRACT FROM AUTHOR]

Summary of main observation and conclusion: A visible light driven Cu(I)‐catalyzed intermolecular oxyamination of electron‐deficient olefins has been achieved by using O‐benzoylhydroxylamines as donors both for amine and oxygen. The transformation properties afford mild conditions and a wide substrate scope, providing access to ester derivatives of β‐amino alcohols with good yields and high regioselectivity. [ABSTRACT FROM AUTHOR]

Summary of main observation and conclusion: A gold(I)‐catalyzed asymmetric intermolecular tandem [3+3]‐cyclization reaction of 2‐(1‐alkynyl)‐2‐ alken‐1‐ones with nitrones has been developed by using Ming‐Phos as a chiral ligand. This method enables access to the stereodivergent synthesis of highly substituted furo[3,4‐d][1,2]oxazines in excellent efficiency and stereoselectivity (up to 99% yield, 99% ee, >20 : 1 dr). [ABSTRACT FROM AUTHOR]