Cobalt‐Catalyzed One‐Pot Asymmetric Difunctionalization of Alkynes to Access Chiral <i>gem</i>‐(Borylsilyl)alkanes

You, Yang’en; Ge, Shaozhong

doi:10.1002/ange.202107405

Cited by 31 publications

(10 citation statements)

References 49 publications

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“…However, transition-metal catalyzed methods for borosilane synthesis are generally limited to one type of silanes (e.g. secondary silanes) [7][8][9][10][11][12][13][14] . It was found that primary, secondary and tertiary silanes were all competent substrates in our transformation, delivering structurally diverse geminal borosilanes effectively (47)(48)(49)(50)(51)(52).…”

Section: Resultsmentioning

confidence: 99%

Photocatalyzed Regioselective Hydrosilylation for the Divergent Synthesis of Geminal and Vicinal Borosilanes

Kong

Zhang

Zhang³

et al. 2022

Preprint

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Geminal and vicinal borosilanes are useful building blocks in synthetic chemistry and material science. Hydrosilylation/ hydroborylation of unsaturated systems offer expedient access to these motifs. In contrast to the well-established transition-metal-catalyzed methods, radical approaches are rarely explored. Herein we report the synthesis of geminal borosilanes from α-selective hydrosilylation of alkenyl boronates via photoinduced hydrogen atom transfer (HAT) catalysis. Mechanistic studies implicate that the α-selectivity originates from a kinetically favored radical addition and an energetically favored HAT process. We further demonstrate selective synthesis of vicinal borosilanes through hydrosilylation of allyl boronates via 1,2-boron radical migration. These strategies exhibit broad scopes across primary, secondary, and tertiary silanes and various boron compounds. The synthetic utility is evidenced by access to multi-borosilanes in a diverse fashion and scaling up by continuous-flow synthesis.

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Section: Resultsmentioning

confidence: 99%

Photocatalyzed Regioselective Hydrosilylation for the Divergent Synthesis of Geminal and Vicinal Borosilanes

Kong

Zhang

Zhang³

et al. 2022

Preprint

View full text Add to dashboard Cite

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“…When the asymmetric functionalization of alkynes is concerned, there are only a handful of reports, which all used terminal alkyne substrates. Through hydrometalation reactions, chiral gem-1,1-disubstitued aminoboryl-, bis-silyl-, or borylsilyl-alkanes were derived via cobalt-or coppercatalyzed difunctionalizations of alkynes (13)(14)(15)(16). Enabled by gold/ organo-cooperative catalysis, terminal alkynes were functionalized with nitrones and alcohols for the asymmetric assembly of cyclic/ acyclic chiral ketones (17,18).…”

Section: Introductionmentioning

confidence: 99%

Asymmetric multifunctionalization of alkynes via photo-irradiated organocatalysis

et al. 2022

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Alkynes represent a family of pivotal and sustainable feedstocks for various industries such as pharmaceuticals, agrochemicals, and materials, and they are widely used as important starting materials for the production of a broad range of chemical entities. Nevertheless, efficient structural elaborations of alkynes in chemical synthesis, especially asymmetric multifunctionalization of alkynes, remain largely unexplored. It is thus imperative to develop new asymmetric synthetic approaches, making use of these richly available chemical feedstocks, and enabling their conversion to value-added chiral molecules. Here, we disclose our findings on highly enantioselective multifunctionalization of alkynes by merging photochemistry and chiral phosphoric acid catalysis. Our reported one-pot synthetic protocol is applicable to all types of alkyne substrates, incorporating all three reactants in a fully atom-economic fashion to produce optically enriched tetrasubstituted triaryl- and diarylmethanes, important structural scaffolds in medicinal chemistry and biological sciences.

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“…Organosilicon compounds are widely used in synthetic chemistry and material science 1 . As a step- and atom-economical approach to synthesize organosilicon compounds, transition-metal catalyzed hydrosilylation of unsaturated C–C bonds such as alkenes 2 – 10 , alkynes 11 – 17 and dienes 18 – 24 , has been extensively studied. However, the study of the selective hydrosilylation of allenes lags behind, probably because of the challenges associated with regioselectivity and stereoselectivity control 25 .…”

Section: Introductionmentioning

confidence: 99%

Copper-catalyzed regio- and stereo-selective hydrosilylation of terminal allenes to access (E)-allylsilanes

Chen

Jiang

et al. 2022

Nat Commun

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Regioselectivity and stereoselectivity control in hydrosilylation of terminal allenes is challeging. Although the selective synthesis of vinylsilanes, branched allylsilanes or linear (Z)-allylsilanes have been achieved, transition-metal catalyzed hydrosilylation of terminal allenes to access (E)-allylsilane is difficult. Herein, we report a copper-catalyzed selective hydrosilylation reaction of terminal allenes to access (E)-allylsilanes under mild reaction conditions. The reaction shows broad substrate scope, representing an efficient method to prepare trisubstituted (E)-allylsilanes through hydrosilylation reaction of allenes and can also be applied in the synthesis of disubstituted (E)-allylsilanes. The mechanism study reveals that the E-selectivity is kinetically controlled by the catalyst but not by the thermodynamically isomerization of the (Z)-isomer.

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Cobalt‐Catalyzed One‐Pot Asymmetric Difunctionalization of Alkynes to Access Chiral gem‐(Borylsilyl)alkanes

Cited by 31 publications

References 49 publications

Photocatalyzed Regioselective Hydrosilylation for the Divergent Synthesis of Geminal and Vicinal Borosilanes

Photocatalyzed Regioselective Hydrosilylation for the Divergent Synthesis of Geminal and Vicinal Borosilanes

Asymmetric multifunctionalization of alkynes via photo-irradiated organocatalysis

Copper-catalyzed regio- and stereo-selective hydrosilylation of terminal allenes to access (E)-allylsilanes

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