Selective CH Borylation of Alkenes by Palladium Pincer Complex Catalyzed Oxidative Functionalization

Selander, Nicklas; Willy, Benjamin; Szabó, Kálmán J.

doi:10.1002/anie.201000690

Cited by 103 publications

(25 citation statements)

References 54 publications

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“…20 4 Examples V and VI illustrate that the boryls in intermediate I do not all have to be Bpin reagent-derived boryls, and may be replaced by similar, strongly donating anionic donors as part of a bidentate ligand. Successful catalytic C-H borylation of alkenes with pincer complexes of Pd has also been reported by Szabo et al 23 and by Iwasawa et al 24 Our group has recently discovered and developed the catalytic dehydrogenative borylation of terminal alkynes (DHBTA) by pincer complexes of Ir and Pd. Some efforts in pincer-ligated Ir-catalyzed arene borylation have been reported.…”

Section: Introductionmentioning

confidence: 86%

High-Turnover Aromatic C–H Borylation Catalyzed by POCOP-Type Pincer Complexes of Iridium

et al. 2016

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The catalytic C-H borylation of arenes with HBpin (pin = pinacolate) using POCOP-type pincer complexes of Ir has been demonstrated, with turnover numbers exceeding 10 000 in some cases. The selectivity of C-H activation was based on steric preferences and largely mirrored that found in other Ir borylation catalysts. Catalysis in the (POCOP)Ir system depends on the presence of stoichiometric quantities of sacrificial olefin, which is hydrogenated to consume the H2 equivalents generated in the borylation of C-H bonds with HBpin. Smaller olefins such as ethylene or 1-hexene were more advantageous to catalysis than sterically encumbered tert-butylethylene (TBE). Olefin hydroboration is a competing side reaction. The synthesis and isolation of multiple complexes potentially relevant to catalysis permitted examination of several key elementary reactions. These experiments indicate that the C-H activation step in catalysis ostensibly involves oxidative addition of an aromatic C-H bond to the three-coordinate (POCOP)Ir species. The olefin is mechanistically critical to gain access to this 14-electron, monovalent Ir intermediate. C-H activation at Ir(I) here is in contrast to the olefin-free catalysis with state-of-the-art Ir complexes supported by neutral bidentate ligands, where the C-H activating step is understood to involve trivalent Ir-boryl intermediates.

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Section: Introductionmentioning

confidence: 86%

High-Turnover Aromatic C–H Borylation Catalyzed by POCOP-Type Pincer Complexes of Iridium

et al. 2016

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“…83:17 (Scheme 6b). [35,36] Over the last decade, other metal complexes involving rhodium, [37] palladium, [38] iron, [39] cobalt, [40] or copper [41] have been effectively employed in this reaction.…”

Section: Synthesis Of E-alkenyl Boronatesmentioning

confidence: 99%

Alkenyl Boronates: Synthesis and Applications

Carreras

Caballero

Pérez

2019

Chemistry An Asian Journal

200

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DedicatedtoProf. GregorioA sensio on the occasion of his 70th birthdayAbstract: Organoboron compounds have become one of the most versatile buildingb locks in organic synthesis owing to their accessible and efficient conversion into many different functional groups.I np articular,a lkenyl boronates have received ag reat deal of attentiona sv ery reactive substrates in Suzuki-Miyaura cross-coupling reactions. Accord-ingly,e fforts towards the development of efficient methods to prepare this type of compound are ongoing. In this contribution, the progress in the search for synthetic routes for alkenylb oronates and their use in av ariety of organic transformationsisa ccounted.

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“…This mini review summarizes examples where arene C–H activation at a Pd IV centre is proposed in both catalytic transformations and in stoichiometric model systems. 4 For some of these systems, clear experimental evidence demonstrates C–H activation at Pd IV while for others, the role of C–H activation at Pd IV is strongly suspected. Both synthetically useful catalytic cycles and mechanistic details are presented and discussed.…”

Section: Introductionmentioning

confidence: 99%

Carbon–hydrogen (C–H) bond activation at Pd^IV: a Frontier in C–H functionalization catalysis

2015

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Selective CH Borylation of Alkenes by Palladium Pincer Complex Catalyzed Oxidative Functionalization

Cited by 103 publications

References 54 publications

High-Turnover Aromatic C–H Borylation Catalyzed by POCOP-Type Pincer Complexes of Iridium

High-Turnover Aromatic C–H Borylation Catalyzed by POCOP-Type Pincer Complexes of Iridium

Alkenyl Boronates: Synthesis and Applications

Carbon–hydrogen (C–H) bond activation at Pd^IV: a Frontier in C–H functionalization catalysis

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Selective CH Borylation of Alkenes by Palladium Pincer Complex Catalyzed Oxidative Functionalization

Cited by 103 publications

References 54 publications

High-Turnover Aromatic C–H Borylation Catalyzed by POCOP-Type Pincer Complexes of Iridium

High-Turnover Aromatic C–H Borylation Catalyzed by POCOP-Type Pincer Complexes of Iridium

Alkenyl Boronates: Synthesis and Applications

Carbon–hydrogen (C–H) bond activation at PdIV: a Frontier in C–H functionalization catalysis

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Carbon–hydrogen (C–H) bond activation at Pd^IV: a Frontier in C–H functionalization catalysis