PolyBorylated Alkenes as Energy‐Transfer Reactive Groups: Access to Multi‐Borylated Cyclobutanes Combined with Hydrogen Atom Transfer Event DOI Creative Commons
Nicole Hanania, Nadim Eghbarieh, Ahmad Masarwa

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(25)

Published: April 11, 2024

Abstract While polyborylated alkenes are being recognized for their elevated status as highly valuable reagents in modern organic synthesis, allowing efficient access to a diverse array of transformations, including the formation C−C and C‐heteroatom bonds, potential energy‐transfer reactive groups has remained unexplored. Yet, this holds key generating elusive biradical species, which can be captured by olefins, thereby leading construction new highly‐borylated scaffolds. Herein, we report designed strategy photosensitized [2+2]‐cycloadditions poly‐borylated with various olefins enabling regioselective synthesis cyclobutane motifs, 1,1‐di‐, 1,1,2‐tri‐, 1,1,2,2‐tetra‐borylated cyclobutanes. In fact, these compounds belong family that presently lacks synthetic pathways. Interestingly, when α‐methylstyrene was used, reaction involves an interesting 1,5‐hydrogen atom transfer (HAT). Mechanistic deuterium‐labeling studies have provided insight into outcome process. addition, cyclobutanes then demonstrated useful selective oxidation processes resulting cyclobutanones γ‐lactones.

Language: Английский

Synthesis of 3-borylated cyclobutanols from epihalohydrins or epoxy alcohol derivatives DOI Creative Commons
Tyler McDonald, Sophie A. L. Rousseaux

Chemical Science, Journal Year: 2022, Volume and Issue: 14(4), P. 963 - 969

Published: Dec. 21, 2022

There is an increasing interest in cyclobutanes within the medicinal chemistry community. Therefore, methods to prepare that contain synthetic handles for further elaboration are of interest. Herein, we report a new approach synthesis 3-borylated cyclobutanols via formal [3 + 1]-cycloaddition using readily accessible 1,1-diborylalkanes and epihalohydrins or epoxy alcohol derivatives. 1-Substituted epibromohydrin starting materials provide access borylated containing substituents at three four positions on cyclobutane core, enantioenriched epibromohydrins lead with high levels enantiospecificity (>98%). Finally, derivatization studies demonstrate utility both OH Bpin handles.

Language: Английский

Citations

13
A general catalytic synthetic strategy for highly strained methylenecyclobutanes and spiromethylenecyclobutanes DOI Creative Commons
Haotian Zhao, Yu Lin, Mingyu Jiang

et al.

Chemical Science, Journal Year: 2023, Volume and Issue: 14(29), P. 7897 - 7904

Published: Jan. 1, 2023

We developed a copper-catalyzed stereoselective strategy for the unified synthesis of borylated methylenecyclobutanes. The versatile boromethylene unit greatly expands their structural diversity and potential in future drug discovery.

Language: Английский

Citations

8
Borylated cyclobutanes via thermal [2 + 2]-cycloaddition DOI Creative Commons

Kateryna Prysiazhniuk,

Олександр Поліщук,

Stanislav Shulha

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(9), P. 3249 - 3254

Published: Jan. 1, 2024

A one-step approach to borylated cyclobutanes from amides of carboxylic acids and vinyl boronates is elaborated. The reaction proceeds via the thermal [2 + 2]-cycloaddition in situ -generated keteniminium salts.

Language: Английский

Citations

2
Boron Enabled Directed [2+2]‐ and Dearomative [4+2]‐Cycloadditions Initiated by Energy Transfer DOI Creative Commons

Souvik Adak,

Partha Sarathi Hazra,

Carter B. Fox

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 7, 2024

A strategy for the photosensitized [2+2]-cycloaddition between styrenyl dihaloboranes and unactivated allylamines to access cyclobutylboronates with control of stereochemistry regiochemistry is presented. The success reaction relies on temporary coordination in situ generated amines under mild conditions. In addition, cyclobutanes varying substitution patterns have been prepared using N-heterocycles as directing group. Manipulation C-B bond allows synthesis a diverse class from simple precursors. Moreover, these reactions lead complex heteroaromatic compounds, which significant utility medicinal chemistry. Finally, dearomative [4+2]-cycloaddition naphthalenes boron-enabled tethering has also uncovered synthesize 3-dimensional borylated building blocks.

Language: Английский

Citations

2
PolyBorylated Alkenes as Energy‐Transfer Reactive Groups: Access to Multi‐Borylated Cyclobutanes Combined with Hydrogen Atom Transfer Event DOI Creative Commons
Nicole Hanania, Nadim Eghbarieh, Ahmad Masarwa

et al.

Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(25)

Published: April 11, 2024

Abstract While polyborylated alkenes are being recognized for their elevated status as highly valuable reagents in modern organic synthesis, allowing efficient access to a diverse array of transformations, including the formation C−C and C‐heteroatom bonds, potential energy‐transfer reactive groups has remained unexplored. Yet, this holds key generating elusive biradical species, which can be captured by olefins, thereby leading construction new highly‐borylated scaffolds. Herein, we report designed strategy photosensitized [2+2]‐cycloadditions poly‐borylated with various olefins enabling regioselective synthesis cyclobutane motifs, 1,1‐di‐, 1,1,2‐tri‐, 1,1,2,2‐tetra‐borylated cyclobutanes. In fact, these compounds belong family that presently lacks synthetic pathways. Interestingly, when α‐methylstyrene was used, reaction involves an interesting 1,5‐hydrogen atom transfer (HAT). Mechanistic deuterium‐labeling studies have provided insight into outcome process. addition, cyclobutanes then demonstrated useful selective oxidation processes resulting cyclobutanones γ‐lactones.

Language: Английский

Citations

1