Catalytic Homologation‐Allylboration Sequence for Diastereo‐ and Enantioselective Synthesis of Densely Functionalized β‐Fluorohydrins with Tertiary Fluoride Stereocenters DOI Creative Commons
Qiang Wang,

Lars Eriksson,

Kálmán J. Szabó

et al.

Angewandte Chemie, Journal Year: 2023, Volume and Issue: 135(19)

Published: March 8, 2023

Abstract Homologation of trisubstituted fluoroalkenes followed by allylboration aldehyde, ketone and imine substrates is suitable for synthesis β‐fluorohydrin amine products. In the presence ( R )‐iodo‐BINOL catalyst enantioselectivities up to 99 % can be achieved formation a single stereoisomer with adjacent stereocenters, which one tertiary C−F center.

Language: Английский

Triethoxysilane-Catalyzed Single and Sequential Regioselective Hydroboration of Terminal Alkynes: Sustainable Access to E-Alkenylboronate and Alkyl Gem-Diboronate Esters by Non-Covalent Interactions DOI

Harleen Kaur,

Himani Ahuja,

Rebeca Arévalo

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 976 - 981

Published: Jan. 1, 2025

Triethoxysilane was found to be an efficient catalyst for the synthesis of E-alkenyl- and alkyl-di-boronate esters by single sequential hydroboration terminal alkynes, respectively, with pinacolborane. Mechanistic studies support that formation diboronate proceeds a double pathway steric electronic profile at Si being key enabling second step. Weak non-covalent interactions involving C≡C or C═C bonds in alkynes alkenylboronate have been identified as responsible substrate activation toward addition HBPin.

Language: Английский

Citations

1
Three-Component Approach to Densely Functionalized Trifluoromethyl Allenols by Asymmetric Organocatalysis DOI Creative Commons
Marie Deliaval, Ramasamy Jayarajan, Lars Eriksson

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(18), P. 10001 - 10006

Published: April 26, 2023

We have developed a new three-component catalytic coupling reaction of alkynyl boronates, diazomethanes, and aliphatic/aromatic ketones in the presence BINOL derivatives. The proceeds with remarkably high enantio- diastereoselectivity (up to three contiguous stereocenters) affording tertiary CF3-allenols single operational step. under mild, neutral, metal-free conditions, which leads level functional group tolerance.

Language: Английский

Citations

16
Mechanism of Asymmetric Homologation of Alkenylboronic Acids with CF3-Diazomethane via Borotropic Rearrangement DOI Creative Commons
Maria Biosca, Kálmán J. Szabó, Fahmi Himo

et al.

The Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 89(7), P. 4538 - 4548

Published: March 25, 2024

Density functional theory calculations have been performed to investigate the mechanism for BINOL-catalyzed asymmetric homologation of alkenylboronic acids with CF3-diazomethane. The reaction proceeds via a chiral BINOL ester acid substrate. reveal complex scenario formation BINOL-alkenylboronate species, which is key intermediate in catalytic process. aliphatic alcohol additive plays an important role reaction. This study provides rationalization stereoinduction step reaction, and enantioselectivity mainly attributed steric repulsion between CF3 group diazomethane reagent γ-substituent catalyst. potential energy surface obtained by analyzed means microkinetic simulations.

Language: Английский

Citations

5
Catalytic Homologation‐Allylboration Sequence for Diastereo‐ and Enantioselective Synthesis of Densely Functionalized β‐Fluorohydrins with Tertiary Fluoride Stereocenters DOI Creative Commons
Qiang Wang,

Lars Eriksson,

Kálmán J. Szabó

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(19)

Published: March 8, 2023

Homologation of trisubstituted fluoroalkenes followed by allylboration aldehyde, ketone and imine substrates is suitable for synthesis β-fluorohydrin amine products. In the presence (R)-iodo-BINOL catalyst enantioselectivities up to 99 % can be achieved formation a single stereoisomer with adjacent stereocenters, which one tertiary C-F center.

Language: Английский

Citations

13
Nitrogen-Based Organofluorine Functional Molecules: Synthesis and Applications DOI
Shuai Liu, Jun Zhou, Lu Yu

et al.

Chemical Reviews, Journal Year: 2025, Volume and Issue: unknown

Published: April 22, 2025

Fluorine and nitrogen form a successful partnership in organic synthesis, medicinal chemistry, material sciences. Although fluorine-nitrogen chemistry has long rich history, this field received increasing interest made remarkable progress over the past two decades, driven by recent advancements transition metal organocatalysis photochemistry. This review, emphasizing contributions from 2015 to 2023, aims update state of art synthesis applications nitrogen-based organofluorine functional molecules chemistry. In dedicated sections, we first focus on fluorine-containing reagents organized according type groups attached nitrogen, including N-F, N-RF, N-SRF, N-ORF. review also covers nitrogen-linked building blocks, catalysts, pharmaceuticals, agrochemicals, underlining these components' broad applicability growing importance modern

Language: Английский

Citations

0
Asymmetric Organocatalytic Homologation: Access to Diverse Chiral Trifluoromethyl Organoboron Species DOI Creative Commons
Ramasamy Jayarajan, Tautvydas Kireilis,

Lars Eriksson

et al.

Chemistry - A European Journal, Journal Year: 2022, Volume and Issue: 28(58)

Published: Aug. 18, 2022

Abstract A broad range of aliphatic, aromatic, and heterocyclic boronic acids were successfully homologated using trifluorodiazoethane in the presence BINOL derivatives to provide corresponding chiral trifluoromethyl containing acid high yields excellent enantioselectivity. The situ conversion transient alcohols or β ‐CF3 carboxylates are also demonstrated.

Language: Английский

Citations

13
Transition-Metal-Free Insertion of Diazo Compounds, N-Arylsulfonylhydrazones or Ylides into Organoboronic Acids or Their Derivatives DOI
Jianbo Wang, Zhicheng Bao

Synlett, Journal Year: 2023, Volume and Issue: 34(18), P. 2071 - 2084

Published: June 5, 2023

Abstract Insertion reactions of carbenes or ylides with organoboronic acids their derivatives have emerged as valuable methods for coupling homologation organoboron compounds under metal-free conditions. The crucial steps these are coordination the electron-rich carbon centers carbene precursors to electron-poor boron center, followed by 1,2-migration corresponding tetracoordinated intermediates. This type unique transformation provides an efficient method construction C–C C–X (X = H, B) bonds. Moreover, C–B bonds generated such transformations can be utilized a handle further derivatization iterative homologations. In this Account, we summarize developments in arena according reactive diazo compound, N-arylsulfonylhydrazone ylide species involved. 1 Introduction 2 Reactions Diazo Compounds 3 N-Arylsulfonylhydrazones 4 Ylides 5 Conclusion

Language: Английский

Citations

7
Photo-Triggered, Copper(II) Chloride-Catalyzed Radical Hydroalkylation and Hydrosilylation of Vinylboronic Esters To Access Alkylboronic Esters DOI
Wei Zhou,

Zhiwen Luo,

Hua Xiao

et al.

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(20), P. 14708 - 14718

Published: Oct. 4, 2023

Alkyl boronic acids and their derivatives constitute vital building blocks in organic synthesis are important motifs identified medicinal chemistry. Herein, we present a phototriggered, CuCl2-catalyzed radical hydroalkylation hydrosilylation of vinylboronic esters to alkylboronic esters. This approach exhibits mild reaction conditions, utilization easily accessible reagents, scalability up gram scale. Further synthetic transformations the products mechanistic studies also demonstrated.

Language: Английский

Citations

4
Triethoxysilane-Catalyzed Sequential Regioselective Hydroboration of Terminal Alkynes: Sustainable Access to E-Alkenylboronate and Alkyl Gem-Diboronate Esters DOI Creative Commons

Harleen Kaur,

Himani Ahuja,

Rebeca Arévalo

et al.

Published: Feb. 12, 2024

The commercial reagent, HSi(OEt)3, was an efficient catalyst for the synthesis of E-alkenylboronate esters and alkyl gem-diboronate by single or double hydroboration terminal alkynes with HBPin (pinacolborane). reaction time controlled whether a addition to occurred. Aromatic containing strong electron-donating -withdrawing substituents at different positions as well aliphatic were efficiently mono- dihydroborated. Mechanistic studies suggested that formation diboronate proceeds second cycle being rate determining. HSi(OEt)3 has been identified deactivation pathway operative in catalysis. Screening other silicon compounds this transformation supported steric electronic profile is key promote step.

Language: Английский

Citations

1
DFT Study in An Asymmetric Organocatalytic Homologation: Mechanism, Origin of Stereoselectivity DOI
Yang Wang, Donghui Wei

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

Published: Oct. 24, 2024

Abstract In the present study, mechanism, origin of stereoselectivity, and role catalyst organocatalytic homologation reaction between phenyl boronate trifluoromethyl diazomethane have been theoretically investigated using density functional theory (DFT) method. Based on calculations, in situ generated ethanol plays significant triggering reaction. Moreover, [1,2]‐boron migration process is stereoselectivity‐determining step, with S ‐configured isomer being predominantly. addition, NCI analysis performed to disclose stereoselectivity.

Language: Английский

Citations

0