Organocatalytic Diboration Involving “Reductive Addition” of a Boron–Boron σ-Bond to 4,4′-Bipyridine

Ohmura, Toshimichi; Morimasa, Yohei; Suginome, Michinori

doi:10.1021/jacs.5b00546

Cited by 63 publications

(56 citation statements)

References 63 publications

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“…In the case of E=B and Si, a subsequent isomerization generates the corresponding 1,4‐addition product whereas addition of another equivalent of HBpin resulted in a second 1,2‐hydroboration to afford the bis‐ N ‐borylated 1,2,3,4‐tetrahydropyrazine. A similar reductive addition of 4,4′‐bipyridines has subsequently been reported using B 2 pin 2 …”

Section: Introductionsupporting

confidence: 68%

The Phosphinoboration of N‐Heterocycles

Geier

Vogels

Mellonie

et al. 2017

Chemistry A European J

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The addition of phosphinoboronate ester Ph PBpin (pin=1,2-O C Me ) (1) to a number of different N-heterocycles has been investigated. Reaction of 1 with pyridine resulted in highly selective formation of the corresponding 1,4-addition product, with addition of the electron-deficient Bpin group to the pyridine nitrogen atom and the phosphido group to the para carbon atom. Conversely, reactions of para-substituted pyridine derivatives occurred predominately to afford 1,2-addition products while quinoline reacted to afford the 1,2-adduct which ultimately isomerized to afford the corresponding 1,4-addition product. Preliminary computational studies have been undertaken to explore possible pathways for these transformations including transfer of the PPh anion from [B(PPh ) pin] to the 4-position of a borenium/boronium activated pyridine and concerted pathways for 1,2-addition via intramolecular nucleophilic attack of PPh at C2 of a Ph PBpin-coordinated pyridine via a four-centered transition state and intramolecular transfer of PPh to the 2-position of a boron-activated pyridine in a phosphido-bridged dimer involving a six-centered transition state.

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Section: Introductionsupporting

confidence: 68%

The Phosphinoboration of N‐Heterocycles

Geier

Vogels

Mellonie

et al. 2017

Chemistry A European J

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“…Recently, 4,4′-bipyridine (bipy) with delocalized -electrons of the pyridyl rings obtains increasing attention in preparing light emitting complexes in different technical applications, such as emitting materials for organic light emitting diodes, sensitizers in solar energy conversion, chemical sensors and so forth [6][7][8][9]. The ability of bipy to act as a rigid, rod-like organic building block in the self-assembly of coordination frameworks is well-known, such as, acting as a charge-compensating cation, a pillar bonding to inorganic skeletal backbone, an uncoordinated guest molecule and organic template, a bridge connecting two metal complex moieties, or linking a metal and an inorganic framework [10][11][12].…”

Section: Introductionmentioning

confidence: 99%

A novel samarium complex with interesting photoluminescence and semiconductive properties

Zhang¹,

Chen²,

F.Wang³

2018

Bull. Chem. Soc. Eth.

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ABSTRACT.[Sm(H2O)4(NO3)3](4,4'-Hbipy)2(NO3)2 (1) (bipy = bipyridine) has been synthesized via hydrothermal reaction and characterized by X-ray diffraction. The title complex features an isolated structure, based on discrete 4,4'-Hbipy moieties, isolated nitrates and [Sm(H2O)4(NO3)3] species. The samarium ion is in a distorted bicapped square antiprism environment, coordinated by three bidentate nitrates and four coordination water molecules. The 4,4'-Hbipy moieties, isolated nitrates and [Sm(H2O)4(NO3)3] species are held together via hydrogen bonds and … interactions to form a 3-D supramolecular framework. Luminescent investigation reveals a strong emission in blue region. Optical absorption spectrum of 1 reveals the presence of an optical gap of 3.60 eV.

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“…[5] Recently,t he Lewis adducts of sp 2 -sp 3 diborane compounds have been reported for the borylation or diboration of unsaturated substrates. [10] Nevertheless,t he mechanistic details of this reaction are unclear yet. In such cases,t he B-(sp 2 ) À B(sp 3 )b onds are always cleaved heterolytically.…”

mentioning

confidence: 97%

“…[5][6][7][8][9] It has been shown that diborane compounds became asource of nucleophilic boryl moiety,w hen one of the boron atoms of the diborane was tetracoordinated to as trong base (Scheme 1a). [10] Nevertheless,t he mechanistic details of this reaction are unclear yet. [6c, 7b] In addition, reductive addition of diboranes to sterically hindered pyrazines in the presence of bipyridine derivatives has also been reported.…”

mentioning

confidence: 99%

Homolytic Cleavage of a B−B Bond by the Cooperative Catalysis of Two Lewis Bases: Computational Design and Experimental Verification

et al. 2016

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Density functional theory (DFT) investigations revealed that 4-cyanopyridine was capable of homolytically cleaving the B-B σ bond of diborane via the cooperative coordination to the two boron atoms of the diborane to generate pyridine boryl radicals. Our experimental verification provides supportive evidence for this new B-B activation mode. With this novel activation strategy, we have experimentally realized the catalytic reduction of azo-compounds to hydrazine derivatives, deoxygenation of sulfoxides to sulfides, and reduction of quinones with B2 (pin)2 at mild conditions.

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Organocatalytic Diboration Involving “Reductive Addition” of a Boron–Boron σ-Bond to 4,4′-Bipyridine

Cited by 63 publications

References 63 publications

The Phosphinoboration of N‐Heterocycles

The Phosphinoboration of N‐Heterocycles

A novel samarium complex with interesting photoluminescence and semiconductive properties

Homolytic Cleavage of a B−B Bond by the Cooperative Catalysis of Two Lewis Bases: Computational Design and Experimental Verification

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