An anti-Markovnikov hydroarylation of unsaturated amides via a Cu/Pd synergistically catalyzed cascade borylation/intramolecular sp
-sp
cross-coupling has been disclosed. 3,4-Dihydroquinolinones, one ...type of important scaffold prevailing in pharmaceuticals and biologically active compounds, could be readily accessible with high regio-selectivity and high yields.
An efficient, transition-metal free, and practical approach to
cis
-bis(boryl)alkenes from various alkynes was disclosed in the presence of a catalytic amount of K
2
CO
3
under mild conditions. ...Meanwhile, tetrasubstituted alkenes and phenanthrene derivatives were readily constructed from the target diborylalkenes via Suzuki-Miyaura cross coupling.
Fluorinated organoboron compounds are important synthetic building blocks that combine the unique characteristics of a fluorinated motif with the versatile synthetic applications of organoboron ...moiety. This review article guides the research on fluorinated organoboron compounds mainly from four aspects in recent years: selective monodefluoroborylation of polyfluoroarenes and polyfluoroalkenes, selective borylation of fluorinated substrates, selective fluorination of organoboron compounds, and borofluorination of alkynes/olefins. In addition, this review will provide a necessary guidance and inspiration for the research on the valuable synthetic building block fluorinated organoboron compounds.
An environmentally benign and convenient method is developed to access a variety of functionalized geminal-diborylalkanes from various electron-deficient alkynes and B2pin2. The reactions proceed via ...the Domino-Borylation–Protodeboronation (DBP) strategy under mild conditions with high regioselectivity, high chemoselectivity, broad functional group tolerance as well as high yields. Meanwhile, further applications of the gem-diboronate products have been explored by silver-catalyzed deboronation–difluorination, base-mediated protodeboronation as well as deborylative secondary alkylation of 2-phenylpyridine N-oxides.
A divergent strategy for precise construction of SCF2H or SeCF2H groups on heteroarenes generated in situ from CF3-containing 1,3-enynes was developed. Reactions of readily available 1,3-enynes with ...S8 and ClCF2H provided 3-SCF2H-4-CF3-thiophenes via a cascade thiophene construction/selective C3 position thiolation/difluoromethylthiolation process, as did a series of 3-SeCF2H-4-CF3-selenophenes by similar strategies. The plausible radical annulation process for the construction of the thiophene ring and difluorocarbene generated in situ was confirmed by experiment.
Since a nucleophilic sp
2
boron species can be generated
in situ
under the combined action of an inorganic base, B
2
pin
2
and methanol, research on base-promoted nucleophilic borylation of ...unsaturated compounds has attracted significant attention. A series of multi-borylated compounds, such as alkyl 1,2-bis(boronates),
gem
-diborylalkanes, and 1,1,2-tris(boronates), are constructed based on this strategy. These multi-borylated compounds can in turn undergo selective protodeboronation, creating a variety of useful boron-containing compounds. This Feature article documents the development of base-promoted domino-borylation-protodeboronation (DBP) strategies and their applications in organic synthesis.
Abundant multi-borylated compounds, such as alkyl 1,2-bis(boronates),
gem
-diborylalkanes and 1,1,2-tris(boronates) are constructed
via
the base-promoted DBP strategies, which can undergo selective protodeboronation, giving many borylated molecules.
A Pd-catalyzed highly regioselective 1,2-difunctionalization of vinylarenes is disclosed in which multisubstituted olefins are efficiently and conveniently constructed under ambient temperature with ...good compatibility and a broad substrate scope. Notably, a quarternary carbon center could be readily built up from 1,1-disubstituted styrenes, which are big challenges in the previous methods.
A divergent strategy for precise construction of SCF
H or SeCF
H groups on heteroarenes generated
from CF
-containing 1,3-enynes was developed. Reactions of readily available 1,3-enynes with S
and ...ClCF
H provided 3-SCF
H-4-CF
-thiophenes via a cascade thiophene construction/selective C3 position thiolation/difluoromethylthiolation process, as did a series of 3-SeCF
H-4-CF
-selenophenes by similar strategies. The plausible radical annulation process for the construction of the thiophene ring and difluorocarbene generated
was confirmed by experiment.
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An expedient and mild strategy for the synthesis of unconventional 2-(dimethylamino)-3,3-difluorochroman-4-one derivatives from o-hydroxyarylenaminones and Selectfluor was developed ...at room temperature under catalyst-free conditions. This method showed excellent chemoselectivity and great functional groups tolerance.
A mild, transition metal-free, diborane-mediated deoxygenation of nitro groups was discovered that in situ generates nitrosoarene reactive intermediates. This new reactivity mode of B2pin2 was ...leveraged to construct indoles from o-nitrostyrenes through a reductive-cyclization reaction that exhibits a Hammett ρ-value of +0.97 relative to σpara values. Our new deoxygenation reaction is efficient, practical, and scaleable, enabling access to a broad range of indoles.
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