Unsymmetrical Diborane(4) Derivatives: A Comparative Study

Borner, Corinna; Wiecha, Maximilian T.

doi:10.1002/ejic.201700545

Cited by 9 publications

(5 citation statements)

References 55 publications

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“…Inspired by the widespread access to copper boryls via Cu‐O/B‐B σ‐bond metathesis reactions, [4,6c–f,8,10] we investigated the reaction of B 2 (OMe) 4 with (6‐Dipp)CuOtBu (Scheme 1). [17] An equimolar mixture of these reagents dissolved in C 6 D 6 provided promising spectroscopic data.…”

Section: Resultsmentioning

confidence: 99%

Acyclic Boryl Complexes of Copper(I)

Charman,

Hobson,

Jackson

et al. 2023

Chemistry A European J

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Reaction of (6‐Dipp)CuOtBu (6‐Dipp = C{NDippCH2}2CH2, Dipp = 2,6‐iPr2C6H3) with B2(OMe)4 provided access to (6‐Dipp)CuB(OMe)2 via σ‐bond metathesis. (6‐Dipp)CuB(OMe)2 was characterised by NMR spectroscopy and X‐ray crystallography and shown to be a monomeric acyclic boryl of copper. (6‐Dipp)CuB(OMe)2 reacted with ethylene and diphenylacetylene to provide insertion compounds into the Cu‐B bond which were characterised by NMR spectroscopy in both cases and X‐ray crystallography in the latter. It was also competent in the rapid catalytic deoxygenation of CO2 in the presence of excess B2(OMe)4. Alongside π‐insertion, (6‐Dipp)CuB(OMe)2 reacted with LiNMe2 to provide a salt metathesis reaction at boron, giving (6‐Dipp)CuB(OMe)NMe2, a second monomeric acyclic boryl, which also cuproborated diphenylacetylene. Computational interrogation validated these acyclic boryl species to be electronically similar to (6‐Dipp)CuBpin.

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Section: Resultsmentioning

confidence: 99%

Acyclic Boryl Complexes of Copper(I)

Charman,

Hobson,

Jackson

et al. 2023

Chemistry A European J

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“…Generally, monoquaternization of sp 2 -sp 2 diboron reagents produces sp 2 -sp 3 diboron reagents. Such transformations have been explored for a long time since it is not only a research interest of main group chemistry, but also the crucial conversion in the activation of various sp 2 -sp 2 borylating reagents [20,21]. The latter process is usually achieved via the assistance of additive, single Lewis bases, which produces lengthened, polarized, and more reactive B–B bonds.…”

Section: Sp2-sp3 Diboron Reagentsmentioning

confidence: 99%

Unsymmetrical Diboron Reagents: Application in Borylation Reactions of Unsaturated Bonds

Ding

Miao

2019

Molecules

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In the past decades, borylation reactions have received extensive research interest and have developed into effective tools in the synthesis of versatile organoboron compounds. Boranes and symmetrical diboron compounds are commonly utilized as borylating reagents in these transformations, especially in the borylation reactions of unsaturated bonds. More recently, several types of unsymmetrical diboron reagents have been synthesized and applied in these borylation reactions, allowing for complementary chemo- and regioselectivity. This review aimed to highlight the recent development in this rising research field, focusing on new reactivity and selectivity that originates from the use of these unsymmetrical diboron reagents.

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“…In contrast, [(IPr)CuBpin] decomposes within hours [23] . Diaminoborane derivatives have also been extensively explored by Kleeberg and co‐workers who reported a range of NHC‐copper diaminoboryls where the varying substitution on both the NHC and boron resulted in either monomeric or, in the case of smaller substituents, dimeric μ‐boryl systems [21,24] . Following the significant effects on stability introduced by the relatively minor substitution of the IPr for 6‐Dipp ligand in a (NHC)CuBpin complex that we recently reported, we set out to investigate whether the 6‐Dipp ligand could support a wider range of dialkoxyboryl fragments at copper.…”

Section: Introductionmentioning

confidence: 99%

Ring‐Expanded N‐Heterocyclic Copper(I) Boryl Complexes: The Structures of [(6‐Dipp)CuBcat], [(6‐Dipp)CuBneop], and [(6‐Dipp)CuBhex]

et al. 2023

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σ-Bond metathesis reactions between [(6-Dipp)CuOtBu] (6-Dipp = :C({Dipp}NCH 2 ) 2 CH 2 , Dipp = 2,6-iPr 2 À C 6 H 3 ) and three diboranes gave access to three new copper(I) boryl complexes [(6-Dipp)CuBcat], [(6-Dipp)CuBneop], and [(6-Dipp)CuBhex] (cat = 1,2-O 2 C 6 H 4 ; neop = (OCH 2 ) 2 C(CH 3 ) 2 ; hex = OC(CH 3 )HCH 2 C-(CH 3 ) 2 O). Whilst [(6-Dipp)CuBcat] and [(6-Dipp)CuBneop] formed rapidly in toluene, access to [(6-Dipp)CuBhex] required heating to 60 °C for days. The complexes were characterised by singlecrystal X-ray crystallography which showed in all three cases that the systems were monomers and distorted-linear at the copper atom. The stability of [(6-Dipp)CuBneop] was found to be comparable to that of [(IPr*)Cu-Bneop] (IPr* = 1,3-bis(2,6-(diphenylmethyl)-4-methylphenyl)imidazol-2-ylidene); it persisted in solution for days with no sign of decomposition. [(6-Dipp)CuBhex] is a rare crystallographically characterised example of a complex containing a boryl anion supported by the hexylene glycolato ligand.

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Unsymmetrical Diborane(4) Derivatives: A Comparative Study

Cited by 9 publications

References 55 publications

Acyclic Boryl Complexes of Copper(I)

Acyclic Boryl Complexes of Copper(I)

Unsymmetrical Diboron Reagents: Application in Borylation Reactions of Unsaturated Bonds

Ring‐Expanded N‐Heterocyclic Copper(I) Boryl Complexes: The Structures of [(6‐Dipp)CuBcat], [(6‐Dipp)CuBneop], and [(6‐Dipp)CuBhex]

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