Stereospecific Conversion of Boronic Esters into Enones using Methoxyallene: Application in the Total Synthesis of 10‐Deoxymethynolide DOI Creative Commons

Kristian J. Chambers,

Patthadon Sanghong,

Daniel Carter Martos

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(50)

Published: Oct. 25, 2023

Abstract Enones are widely utilized linchpin functional groups in chemical synthesis and molecular biology. We herein report the direct conversion of boronic esters into enones using commercially available methoxyallene as a three‐carbon building block. Following boronate complex formation by reaction ester with lithiated‐methoxyallene, protonation triggers stereospecific 1,2‐migration before oxidation generates enone. The protocol shows broad substrate scope complete enantiospecificity is observed chiral migrating groups. In addition, various electrophiles could be used to induce give much broader range α‐functionalized enones. Finally, methodology was applied 14‐step enone‐containing polyketide 10‐deoxymethynolide.

Language: Английский

Rhodium-Catalyzed Desymmetric Arylation of γ,γ-Disubsituted Cyclohexadienones: Asymmetric Synthesis of Chiral All-Carbon Quaternary Centers DOI

Yu Qiao,

Shiming Bai,

Xiaofeng Wu

et al.

Organic Letters, Journal Year: 2022, Volume and Issue: 24(7), P. 1556 - 1560

Published: Feb. 10, 2022

The desymmetric arylation of prochiral cyclohexadienones with ArZnCl in the presence an (R)-segphos–rhodium catalyst gave high yields corresponding cyclohexenones, which contain a chiral arylated carbon center at β-position and all-carbon quaternary γ-position, diastereo- enantioselectivities. This catalytic system was also applied to spirocarbocyclic afforded cyclohexenones bearing spiro dr ee.

Language: Английский

Citations

10

Doyle–Kirmse reaction using 3,3-difluoroallyl sulfide and N-sulfonyl-1,2,3-triazole: an efficient access to gem-difluoroallylated multifunctional quaternary carbon DOI

Jiazhuang Wang,

Jingwen Yu, Junyu Chen

et al.

Organic & Biomolecular Chemistry, Journal Year: 2021, Volume and Issue: 19(32), P. 6974 - 6978

Published: Jan. 1, 2021

A Doyle-Kirmse reaction of N-sulfonyl-1,2,3-triazole with 3,3-difluoroallyl sulfide through a Rh(ii)-catalyzed [2,3]-sigmatropic rearrangement has been developed, which provides an efficient access to multifunctional quaternary centers containing aryl, imino, thio, and brominated gem-difluoroallyl groups. The features broad substrate scope moderate excellent yields. applicability the method is confirmed by gram-scale synthesis further transformations.

Language: Английский

Citations

13

Access to Ketones through Palladium‐Catalyzed Cross‐Coupling of Phenol Derivatives with Nitroalkanes Followed by Nef Reaction DOI

Xiaoyu He,

Sengui Hu,

Yuxuan Xiao

et al.

European Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 2022(35)

Published: Aug. 6, 2022

Abstract A practical protocol for the synthesis of ketones by Pd‐catalyzed cross‐coupling phenol derivatives with nitroalkanes followed a Nef‐type reaction has been developed. The readily available served as alkyl nucleophiles under basic conditions to couple easy‐to‐handle derived from naturally abundant phenols. avoidance using organometallics and organic halides makes this more sustainable. was compatible various functional groups, including nitro, cyano, acetyl, aldehyde, halide, ester groups. Furthermore, successful application our method in drug exemplified its synthetic potential pharmaceutical sciences. Preliminary mechanistic investigations strongly suggested possible involvement α‐aryl‐substituted nitroalkane intermediates.

Language: Английский

Citations

9

Finding activity through rigidity: syntheses of natural products containing tricyclic bridgehead carbon centers DOI
Zhi Xu, Xin Li,

John A. Rose

et al.

Natural Product Reports, Journal Year: 2023, Volume and Issue: 40(8), P. 1393 - 1431

Published: Jan. 1, 2023

This review summarizes the syntheses of ten representative families natural products that contain tricyclic bridgehead carbon centers (TBCCs). We organize approaches around five strategies shown to aid future synthetic endeavors.

Language: Английский

Citations

5

Stereospecific Conversion of Boronic Esters into Enones using Methoxyallene: Application in the Total Synthesis of 10‐Deoxymethynolide DOI Creative Commons

Kristian J. Chambers,

Patthadon Sanghong,

Daniel Carter Martos

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(50)

Published: Oct. 25, 2023

Abstract Enones are widely utilized linchpin functional groups in chemical synthesis and molecular biology. We herein report the direct conversion of boronic esters into enones using commercially available methoxyallene as a three‐carbon building block. Following boronate complex formation by reaction ester with lithiated‐methoxyallene, protonation triggers stereospecific 1,2‐migration before oxidation generates enone. The protocol shows broad substrate scope complete enantiospecificity is observed chiral migrating groups. In addition, various electrophiles could be used to induce give much broader range α‐functionalized enones. Finally, methodology was applied 14‐step enone‐containing polyketide 10‐deoxymethynolide.

Language: Английский

Citations

5