Photo-Induced<i>ortho</i>-C–H Borylation of Arenes through In Situ Generation of Rhodium(II) Ate Complexes

Tanaka, Jin; Nagashima, Yuki; Dias, Antônio Junio Araujo; Tanaka, Ken

doi:10.1021/jacs.1c05859

Cited by 39 publications

(18 citation statements)

References 48 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…In 2021, Tanaka and co-workers reported the related photoinduced C–H borylation catalyzed by Rh III -cyclopentadienyl complex 17 (Scheme 4 B). 23 However, in contrast to the previous study by Baslé, the photoinduction is required to reduce the metal after the addition of the C–H bond to form a Rh II -ate complex that facilitates the ligand exchange with B 2 pin 2 . Key to enhanced yields was the use of [Ir(dFppy) 3 ] as photoredox catalyst.…”

Section: Trends In C–h Borylation Reactionsmentioning

confidence: 91%

Recent Trends in Group 9 Catalyzed C–H Borylation Reactions: Different Strategies To Control Site-, Regio-, and Stereoselectivity

Veth¹,

Grab²,

Dydio³

2021

Synthesis

View full text Add to dashboard Cite

Organoboron compounds continue contributing substantially to advances in organic chemistry with their increasing role as both synthetic intermediates and target compounds for medicinal chemistry. Particularly attractive methods of their synthesis are based on the direct borylation of C−H bonds of available starting materials since no additional pre-functionalization steps are required. However, due to the high abundance of C−H bonds with similar reactivity in organic molecules, synthetically useful C−H borylation protocols demand sophisticated strategies to achieve high regio- and stereoselectivity. For this purpose, selective transition-metal-based catalysts have been developed, with group 9-centered catalysts being among the most commonly utilized. Recently, a multitude of diverse strategies has been developed to push the boundaries of C−H borylation reactions with respect to their regio- and enantioselectivity. Herein, we provide an overview of approaches for the C−H borylation of arenes, alkenes, and alkanes based on group 9-centered catalysts with a focus on the recent literature. Lastly, an outlook is given to assess the future potential of the field.

show abstract

Section: Trends In C–h Borylation Reactionsmentioning

confidence: 91%

Recent Trends in Group 9 Catalyzed C–H Borylation Reactions: Different Strategies To Control Site-, Regio-, and Stereoselectivity

Veth¹,

Grab²,

Dydio³

2021

Synthesis

View full text Add to dashboard Cite

show abstract

“…The cyclometalated complex can then undergo photoexcitation to access a triplet intermediate, which engages in single electron transfer reactions. [43]…”

Section: Claire Empel Studied Chemistry At Rwth Aachen University And...mentioning

confidence: 99%

“…This reaction proceeds via the in situ formation of a Rh I complex that undergoes cyclometalation. The cyclometalated complex can then undergo photoexcitation to access a triplet intermediate, which engages in single electron transfer reactions [43] …”

Section: Light‐mediated C−h Metalationmentioning

confidence: 99%

Visible‐Light‐Induced, Single‐Metal‐Catalyzed, Directed C−H Functionalization: Metal‐Substrate‐Bound Complexes as Light‐Harvesting Agents

2022

View full text Add to dashboard Cite

CÀ H functionalization represents one of the most rapidly advancing areas in organic synthesis and is regarded as one of the key concepts to minimize the ecological and economic footprint of organic synthesis. The ubiquity and low reactivity of CÀ H bonds in organic molecules, however, poses several challenges, and often necessitates harsh reaction conditions to achieve this goal, although it is highly desirable to achieve CÀ H functionalization reactions under mild conditions. Recently, several reports uncovered a conceptually new approach towards CÀ H functionalization, where a single transition-metal complex can be used as both the photosensitizer and catalyst to promote CÀ H bond functionalization in the absence of an exogeneous photosensitizer. In this Minireview, we will provide an overview on recent achievements in CÀ H functionalization reactions, with an emphasis on the photochemical modulation of the reaction mechanism using such catalysts.

show abstract

“…Furthermore, the detailed mechanisms for the substrate-dependent acceleration in the oxidative olefination and annulation reactions using the Cp E and Cp ligands are not clarified . As with the conventional Cp*Rh(III) catalyst, the detailed theoretical mechanistic studies of the Cp E Rh(III) and CpRh(III) catalysts are valuable for an accurate understanding of their properties and development of further catalytic reactions using the electron-deficient CpRh(III) complexes …”

Section: Introductionmentioning

confidence: 99%

Acceleration Mechanisms of C–H Bond Functionalization Catalyzed by Electron-Deficient CpRh(III) Complexes

et al. 2021

Self Cite

View full text Add to dashboard Cite

A rhodium(III) complex bearing a 1,3-bis(ethoxycarbonyl)-substituted or an unsubstituted cyclopentadienyl ligand (Cp E or Cp) significantly accelerates a variety of oxidative C−H bond functionalization reactions. However, the driving force of the acceleration compared with a conventionally used Cp*Rh(III) complex has not been elucidated. Herein, we performed density functional theory (DFT) calculations of the rhodium(III)-catalyzed oxidative C−H bond olefination and annulation reactions using Cp*, Cp, and Cp E ligands, which revealed that the Cp E Rh(III) complex stabilizes transition states of not only a C−H bond activation step but also rate-determining reductive elimination and insertion steps by strong orbital interactions. For the sterically demanding substrates, the less sterically hindered CpRh(III) complex can stabilize the transition states of the reductive elimination step more than the Cp E Rh(III) complex. Moreover, the whole reaction pathways were calculated to elucidate the mechanism and selectivity of the oxidative [4 + 2] and [2 + 2 + 2] annulation reactions under cationic and neutral conditions, respectively.

show abstract

Photo-Inducedortho-C–H Borylation of Arenes through In Situ Generation of Rhodium(II) Ate Complexes

Cited by 39 publications

References 48 publications

Recent Trends in Group 9 Catalyzed C–H Borylation Reactions: Different Strategies To Control Site-, Regio-, and Stereoselectivity

Recent Trends in Group 9 Catalyzed C–H Borylation Reactions: Different Strategies To Control Site-, Regio-, and Stereoselectivity

Visible‐Light‐Induced, Single‐Metal‐Catalyzed, Directed C−H Functionalization: Metal‐Substrate‐Bound Complexes as Light‐Harvesting Agents

Acceleration Mechanisms of C–H Bond Functionalization Catalyzed by Electron-Deficient CpRh(III) Complexes

Contact Info

Product

Resources

About