Interaction of E-2-dibutylboryl-1-phenyl-1-diphenylphosphinohex-1-ene with diphenylketene and benzoyl(phenyl)diazomethane

Balueva, A. S.; Mustakimov, E. R.; Nikonov, G. N.; Pisarevskii, A. P.; Struchkov, Yu. T.; Литвинов, И. А.; Musin, R. R.

doi:10.1007/bf01457788

Cited by 10 publications

(2 citation statements)

References 3 publications

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“…29 FLPs have been reported to activate small molecules such as H 2 , alkene, CO 2 , RSSR, carbonyls, etc. [30][31][32][33][34][35][36][37][38][39][40][41][42][43][44] Polyfunctional ambiphilic molecules have been shown to stabilize transition metals. [45][46][47][48][49][50][51][52][53] The electrophilic center of the ambiphilic ligand can accept electron density from the transition metal.…”

Section: Introductionmentioning

confidence: 99%

Reactivity of the Bifunctional Ambiphilic Molecule 8-(dimesitylboryl)quinoline: Hydrolysis and Coordination to CuI, AgI and PdII

2010

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The ambiphilic molecule 8-(dimesitylboryl)quinoline (1) was synthesized by treatment of 8-bromoquinoline or 8-iodoquinoline with n-BuLi followed by dimesitylboronfluoride. Hydrolysis of 1 is unusually rapid compared to bulky triorganoboranes with the sequential loss of mesitylene and formation of mesityl(quinolin-8-yl)borinic acid (2) and 8-quinoline boronic acid dimer (3). Cooperativity within the bifunctional ambiphilic site leads to water activation and protodeboronation of the B-C(Mes) bonds. Blocking of the ambiphilic site of 1 by methylation of the quinoline nitrogen atom leads to an air-stable N-methyl-quinolinium salt. Coordination complexes were formed by reaction of 1 with CuCl, Ag(OTf), and PdCl(2)(PhCN)(2) with coordination of the quinolinyl nitrogen to the metal ion. The Cu(I) and Ag(I) centers are stabilized by η(3)-BC(ipso)C(ortho)π-interaction. The isolated Pd(II) complex is a product of cyclometalation, resulting from elimination of HCl upon deprotonation of the ortho-methyl group of nearby mesityl. The bonding in 7 could be understood as a 16-electron Pd complex that features an anionic η(3)-C(ipso)-C(ortho)-C(benzyl) allylic ligand fragment plus a Pd→B bond, or an η(4)-BC(ipso)-C(ortho)-C(benzyl) boratabutadiene anion fragment.

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Section: Introductionmentioning

confidence: 99%

Reactivity of the Bifunctional Ambiphilic Molecule 8-(dimesitylboryl)quinoline: Hydrolysis and Coordination to CuI, AgI and PdII

2010

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“…7 Reaction of 2-pyridylaminodiorganoborane with isocyanate led to a chelate structure in which the pyridine N-atom was donor to the isocyanate C-atom, and a boron-oxygen bond was formed that completed the six-member ring. 8,9 Balueva and coworkers reported 1,2-borylphosphinoethene reacted with small polar molecules such as ketene, diazo compounds, 10 ketenimine, 11 carbodiimide, isothiocyanate, 12 acetyl chloride, 13 aldehyde, 14,15 oxygen, carbon disulfide, 16 isocyanate, 17 thiocyanate, 18 sulfur and selenium; 19 though, it was unreactive toward nitriles and ketones. We synthesized a family of 2-( picolyl)boranes, 2-( picolyl)-BR 2 (R = Et, Ph; BR 2 = 9-borafluorenyl, 9-borabicyclononane (BBN)).…”

Section: Introductionmentioning

confidence: 99%

1,2-Nucleophilic addition of 2-(picolyl)organoboranes to nitrile, aldehyde, ketone, and amide

Son

Hoefelmeyer

2012

Org. Biomol. Chem.

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A series of 2-(picolyl)borane molecules were synthesized as products of the reaction between 2-(picolyl)lithium and R(2)BOMe (R = ethyl, 9-BBN, phenyl, 9-borafluorenyl). The 2-(picolyl)boranes were dimeric; whereas, monomers coordinated to LiOMe could be isolated when the synthesis was carried out in the presence of TMEDA and THF. The 2-(picolyl)boranes undergo reaction with nitriles, ketones, aldehydes, and amides with apparent 1,2-addition of the B-C(picolyl) bond to the unsaturated bond. Theoretical models reveal the presence of a donor orbital on the 2-(picolyl)borane with significant electron density at the benzylic carbon that we conclude was involved in nucleophilic attack on the electrophilic center of unsaturated organic functional groups.

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Frustrierte Lewis‐Paare: metallfreie Wasserstoffaktivierung und mehr

2009

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Die Kombination sterisch gehinderter Lewis‐Säuren und ‐Basen führt nicht zur üblichen Neutralisationsreaktion unter Bildung der “klassischen” Lewis‐Säure/Base‐Addukte. Stattdessen stehen die Lewis‐Acidität und ‐Basizität solcher “frustrierten Lewis‐Paare” (FLPs) gemeinsam für die Durchführung ungewöhnlicher Reaktionen zur Verfügung. Typische Beispiele für FLPs bestehen aus inter‐ und intramolekularen Kombinationen sperriger Phosphine und Amine mit stark elektrophilen RB(C6F5)2‐Komponenten. Viele frustrierte Lewis‐Paare sind in der Lage, Wasserstoff heterolytisch zu spalten. Die resultierenden H+/H−‐Paare (z. B. stabilisiert in Form der entsprechenden Phosphonium‐Kation/Hydridoborat‐Anion‐Salze) fungieren als metallfreie Katalysatoren für die Hydrierung sperriger Imine, Enamine, Enolether usw. FLPs reagieren auch mit Alkenen, Carbonylverbindungen und einer Vielzahl anderer kleiner Moleküle, darunter auch Kohlendioxid, in vermutlich kooperativen Dreikomponentenreaktionen. Auf dieser Beobachtung lassen sich neue Synthesestrategien aufbauen.

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Interaction of E-2-dibutylboryl-1-phenyl-1-diphenylphosphinohex-1-ene with diphenylketene and benzoyl(phenyl)diazomethane

Cited by 10 publications

References 3 publications

Reactivity of the Bifunctional Ambiphilic Molecule 8-(dimesitylboryl)quinoline: Hydrolysis and Coordination to CuI, AgI and PdII

Reactivity of the Bifunctional Ambiphilic Molecule 8-(dimesitylboryl)quinoline: Hydrolysis and Coordination to CuI, AgI and PdII

1,2-Nucleophilic addition of 2-(picolyl)organoboranes to nitrile, aldehyde, ketone, and amide

Frustrierte Lewis‐Paare: metallfreie Wasserstoffaktivierung und mehr

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