Isolation of a triborylmethide salt

Matteson, Donald S.; Hagelee, Leon A.; Wilcsek, Robert J.

doi:10.1021/ja00796a079

Cited by 25 publications

(7 citation statements)

References 1 publication

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“…A parallel for this is seen in the rearrangement of (E)-benzalacetophenone oxide with excess boron trifluoride etherate to give a mixture of ihreo-3-fluoro-2-hydroxy-l,3-diphenyl-l-propanone and -formyldeoxybenzoin. 16 In the presence of excess boron trifluoride etherate the fluorohydrin is converted directly to -formyldeoxybenzoin, the rearrangement product formed as a result of benzoyl migration. Kinetic examination26 of this process did not permit a distinction between direct conversion of the epoxy ketone to the rearrangement product as opposed to involvement of the fluorohydrin as an obligatory intermediate in the rearrangement.…”

Section: Resultsmentioning

confidence: 99%

Reaction of tertiary glycidamides with boron trifluoride etherate. Evaluation of the potential for rearrangement with amide group migration

Butke¹,

Jimenz²,

Michalik³

et al. 1978

J. Org. Chem.

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with TLC on silica gel with dimethylformamide (Rf 0.9) or aqueous 80% methanol (Rf 0.8). Attempted recrystallization usually resulted in partial decomposition, as shown by TLC. The analytical sample was dried for 9 h at 0.1 Torr at 100 °C. The compound darkened above 240 °C but did not melt up to 400 °C; 100-MHz !H NMR (Me2SO-d8) 8.55 (s, 1, NCHN), 8.10 (s, 1, CH=CB2), 7.64 (broadened s, 1, NH), 7.18 (broadened s, 1, NH), 3.42 (s, ~10, NH, BOH, and H20 from solvent); on addition of methanol dropwise, the 7.64 peak broadened, shifted downfield, and disappeared, and the 7.18 peak broadened somewhat without shifting; NMR (CD3OD)8.31 (brd s.

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Section: Resultsmentioning

confidence: 99%

Reaction of tertiary glycidamides with boron trifluoride etherate. Evaluation of the potential for rearrangement with amide group migration

Butke¹,

Jimenz²,

Michalik³

et al. 1978

J. Org. Chem.

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“…Rathke and Kow [13a] reported next the condensation of the lithium borylmethide salt 2 with cyclohexanone to produce methylenecyclohexane 40 (Scheme 20b). Matteson and co‐workers expanded the general access to α‐mono‐ and α‐polyboryl carbanions and proved their reactivity through similar condensation sequences to those in Scheme 20 [57–63] …”

Section: Reactivity Of Borata‐alkene Compoundsmentioning

confidence: 97%

Borata‐Alkene Species as Nucleophilic Reservoir

2021

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α‐Monoboryl anions show remarkable stability due to the valence deficiency of the adjacent three‐coordinate boron center and can be expressed as its resonance form, the borata‐alkene systems [R2B=CH2]−. The diversity of synthetic approaches as well as the properties of the C=B bond are disclosed in this review, dealing with both electronic and structural properties of the boryl moieties involved. Full characterization in solid state by X‐ray diffraction demonstrated the short distances between B and C, as a consequence of the boron ylide character in the boron‐stabilized carbanions. This review includes a collection of C−B length distances as well as 11B NMR data that can be useful for diagnostic evidence of the partial boron‐carbon double‐bond character. Natural bond orbital (NBO) analysis on DFT computed structures also supports and justifies the borata‐alkene character. The reactivity of the C=B bond acting as nucleophilic synthon is unveiled through extensive electrophilic trapping examples. The homologation protocols with diborylmethane, via single carbon chain extension, involves a facile introduction of the C(sp3)−B bonds, which can be subsequently transformed into functionalized target products, containing C−O, C−N or C−C bonds.

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“…Anionic bisdiborane compounds derived from methanetetraboronic (64) and methanetriboronic esters, 57 -63 gemdiborylalkanes, 26,29,64 and deprotonation of trialkylboranes 65,66 have been found useful in a variety of syntheses, including condensation with aldehydes and ketones, and alkylation by alkyl halides. 67 Matteson et al 68 101 is a very strong base and abstracts protons from dimethyl sulfoxide, in which it is soluble. The lithium salt of 98 is a slightly soluble in THF and precipitates, giving an apparent increase of the acidity of 97, which reacts with bases Y − to form borate complexes 105 or the self-condensation product 104 (Scheme 30).…”

Section: Main Group Metal Compoundsmentioning

confidence: 99%

Recent developments in bisdiborane chemistry: BCB, BCCB, BCCB and BCCB compounds

Dembitsky

Ali

Srebnik

2003

Applied Organom Chemis

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An overview of the development of new strategies in organic synthesis with a minimum of chemical steps is becoming increasingly necessary for the efficient assembly of complex molecular structures. Therefore, the combination of multiple reactions in a single operation represents a particularly efficient approach. Among these strategies, the synthesis and reactivity of bisdiboranes has never been reviewed although its popularity for the synthesis of complex architectural molecules has been steadily increasing during the last decade. This review is intended to highlight the use of partly geminated boranes (B-C-B), and also bisdiborane reagents (B-C-C-B, B-C C-B, B-C C-B).

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Isolation of a triborylmethide salt

Cited by 25 publications

References 1 publication

Reaction of tertiary glycidamides with boron trifluoride etherate. Evaluation of the potential for rearrangement with amide group migration

Reaction of tertiary glycidamides with boron trifluoride etherate. Evaluation of the potential for rearrangement with amide group migration

Borata‐Alkene Species as Nucleophilic Reservoir

Recent developments in bisdiborane chemistry: BCB, BCCB, BCCB and BCCB compounds

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