Diborodichloromethane as Versatile Reagent for Chemodivergent Synthesis of gem‐Diborylalkanes DOI

Tongchang Fang,

Liwei Wang, Miaomiao Wu

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 136(3)

Published: Dec. 8, 2023

Abstract The development of boron reagents is crucial for synthetic chemistry. Herein, we present a scalable and practical synthesis diborodichloromethane (DBDCM) through the reaction trichloromethyllithium with bis(pinacolato)diboron (B 2 pin ). resulting DBDCM reagent serves as basic unit construction various structurally diverse gem ‐diborylalkanes controllable C−Cl functionalizations. Moreover, have developed consecutive tetra‐functionalizations tertiary quaternary carbon containing molecules. use isotopically enriched 13 C‐chloroform 10 B enables C‐DBDCM B‐DBDCM reagents, which are beneficial convenient carbon‐13 boron‐10

Language: Английский

Diborodichloromethane as Versatile Reagent for Chemodivergent Synthesis of gem‐Diborylalkanes DOI

Tongchang Fang,

Liwei Wang, Miaomiao Wu

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 63(3)

Published: Dec. 8, 2023

Abstract The development of boron reagents is crucial for synthetic chemistry. Herein, we present a scalable and practical synthesis diborodichloromethane (DBDCM) through the reaction trichloromethyllithium with bis(pinacolato)diboron (B 2 pin ). resulting DBDCM reagent serves as basic unit construction various structurally diverse gem ‐diborylalkanes controllable C−Cl functionalizations. Moreover, have developed consecutive tetra‐functionalizations tertiary quaternary carbon containing molecules. use isotopically enriched 13 C‐chloroform 10 B enables C‐DBDCM B‐DBDCM reagents, which are beneficial convenient carbon‐13 boron‐10

Language: Английский

Citations

25
Synthesis of substituted benzylboronates by light promoted homologation of boronic acids with N-sulfonylhydrazones DOI Creative Commons
Álvaro Valdés-Maqueda, Lucía López, Manuel Plaza

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(47), P. 13765 - 13775

Published: Jan. 1, 2023

The homologation of boronic acids with diazoalkanes obtained by photochemical decomposition N -tosylhydrazones leads to substituted benzylboronates, previously unavailable under thermal conditions. Batch and continuous flow reactions are described.

Language: Английский

Citations

13
Asymmetric synthesis of atropisomers featuring cyclobutane boronic esters facilitated by ring-strained B-ate complexes DOI Creative Commons

Yu-Wen Sun,

Jingkun Zhao,

Xinyu Yan

et al.

Nature Communications, Journal Year: 2024, Volume and Issue: 15(1)

Published: Dec. 30, 2024

The strain-release-driven reactions of bicyclo[1.1.0]butanes (BCBs) have received significant attention from chemists. Notably, 1,2-migratory enabled by BCB-derived B-ate complexes effectively complement the initiated common BCBs. desired products are particularly valuable for late-stage transformations due to presence C-B bond. However, asymmetric mediated boronate progressed slowly. In this study, we develop an synthesis atropisomers featuring cis-cyclobutane boronic esters facilitated 1,2-carbon or boron migration ring-strained complexes, achieving high enantioselectivity. reaction is compatible with various aryl, alkenyl, alkyl and B

Language: Английский

Citations

4
Transition metal-catalyzed reactivity of carbenes with boronic acid derivatives for arylation (alkylation) and beyond DOI
Akanksha Babbar, Pokhriyal Yamini, Mohammad Saleem

et al.

Organic & Biomolecular Chemistry, Journal Year: 2023, Volume and Issue: 21(35), P. 7062 - 7078

Published: Jan. 1, 2023

This review summarizes the transition metal-catalyzed reactivity of carbenes with different boronic acids and esters to form carbon–carbon bonds, carbon–boron beyond.

Language: Английский

Citations

5
Synthesis of substituted benzylboronates by light promoted homologation of boronic acids with N-sulfonylhydrazones DOI Creative Commons
Álvaro Valdés-Maqueda, Lucía López, Manuel Plaza

et al.

Published: Sept. 12, 2023

The synthesis of benzylboronates by photochemical homologation boronic acids with N-sulfonylhydrazones under basic conditions is described. reaction involves the photolysis N-tosylhydrazone salt to give a diazoalkane followed geminal carboborylation diazoalkane. Under mild conditions, protodeboronation unstable benzylboronic acid circumvented and pinacolboronates can be isolated after pinacol. metholodogy has been applied reactions alkylboronic N-tosylhydrazones aromatic aldehydes ketones, arylboronic aliphatic ketones. Moreover, employment DBU/DIPEA bases combination allows for homogeneous which have adapted continuous flow conditions. Additionally, synthetic versatility boronates enables their further transformation via Csp3-C or Csp3-X bond forming converting this methodology into novel method difunctionalization carbonyls N-tosylhydrazones.

Language: Английский

Citations

2
Synthesis of Carboxylic Acids Containing α-All-Carbon Quaternary Centers from Diazo Compounds and Trialkylboranes DOI
Yuan‐Ze Xu, Yan Xu, Jianbo Wang

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 26, 2024

The construction of C–C bonds to form all-carbon quaternary centers remains a significant challenge in synthetic chemistry. Herein, we report tandem process involving 1,2-migration tetra-coordinated boron intermediate followed by Claisen rearrangement the enolate, achieved through reaction between allyl diazoacetates and trialkylboranes. transformation forms two at carbenic position diazo substrate single-step operation under neutral conditions. Using this method, successfully realized gram-scale formal total synthesis Vincamine, an indole alkaloid with pharmacological activity.

Language: Английский

Citations

0
Diborodichloromethane as Versatile Reagent for Chemodivergent Synthesis of gem‐Diborylalkanes DOI

Tongchang Fang,

Liwei Wang, Miaomiao Wu

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 136(3)

Published: Dec. 8, 2023

Abstract The development of boron reagents is crucial for synthetic chemistry. Herein, we present a scalable and practical synthesis diborodichloromethane (DBDCM) through the reaction trichloromethyllithium with bis(pinacolato)diboron (B 2 pin ). resulting DBDCM reagent serves as basic unit construction various structurally diverse gem ‐diborylalkanes controllable C−Cl functionalizations. Moreover, have developed consecutive tetra‐functionalizations tertiary quaternary carbon containing molecules. use isotopically enriched 13 C‐chloroform 10 B enables C‐DBDCM B‐DBDCM reagents, which are beneficial convenient carbon‐13 boron‐10

Language: Английский

Citations

0