Expanding Chemical Space One Carbocycle at a Time DOI

Synfacts, Journal Year: 2024, Volume and Issue: 20(09), P. 0994 - 0994

Published: Aug. 16, 2024

Language: Английский

Palladium-catalyzed decarboxylative (4 + 3) cycloadditions of bicyclobutanes with 2-alkylidenetrimethylene carbonates for the synthesis of 2-oxabicyclo[4.1.1]octanes DOI Creative Commons

X. N. Gao,

Lei Tang, Xu Zhang

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(34), P. 13942 - 13948

Published: Jan. 1, 2024

While cycloaddition reactions of bicyclobutanes (BCBs) have emerged as a potent method for synthesizing (hetero-)bicyclo[

Language: Английский

Citations

24
Zinc‐Catalyzed Enantioselective Formal (3+2) Cycloadditions of Bicyclobutanes with Imines: Catalytic Asymmetric Synthesis of Azabicyclo[2.1.1]hexanes DOI Open Access
Feng Wu, Wen‐Biao Wu, Yuanjiu Xiao

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(48)

Published: Sept. 2, 2024

Abstract The cycloaddition reaction involving bicyclo[1.1.0]butanes (BCBs) offers a versatile and efficient synthetic platform for producing C(sp 3 )‐rich rigid bridged ring scaffolds, which act as phenyl bioisosteres. However, there is scarcity of catalytic asymmetric cycloadditions BCBs to fulfill the need enantioenriched saturated bicycles in drug design development. In this study, an synthesis valuable azabicyclo[2.1.1]hexanes (aza‐BCHs) by enantioselective zinc‐catalyzed (3+2) with imines reported. proceeds effectively novel type BCB that incorporates 2‐acyl imidazole group diverse array alkynyl‐ aryl‐substituted imines. target aza‐BCHs, consist α‐chiral amine fragments two quaternary carbon centers, are efficiently synthesized up 94 % 96.5:3.5 er under mild conditions. Experimental computational studies reveal follows concerted nucleophilic ring‐opening mechanism This distinct from previous on Lewis acid‐catalyzed BCBs.

Language: Английский

Citations

24
Divergent Synthesis of Sulfur‐Containing Bridged Cyclobutanes by Lewis Acid Catalyzed Formal Cycloadditions of Pyridinium 1,4‐Zwitterionic Thiolates and Bicyclobutanes DOI
Yuanjiu Xiao, Feng Wu, Lei Tang

et al.

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

Published: May 31, 2024

Bridged cyclobutanes and sulfur heterocycles are currently under intense investigation as building blocks for pharmaceutical drug design. Two formal cycloaddition modes involving bicyclobutanes (BCBs) pyridinium 1,4-zwitterionic thiolate derivatives were described to rapidly expand the chemical space of sulfur-containing bridged cyclobutanes. By using Ni(ClO

Language: Английский

Citations

19
Facile access to bicyclo[2.1.1]hexanes by Lewis acid-catalyzed formal cycloaddition between silyl enol ethers and bicyclo[1.1.0]butanes DOI Creative Commons

Sai Hu,

Yuming Pan,

Dongshun Ni

et al.

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

Published: July 20, 2024

Abstract Saturated three-dimensional carbocycles have gained increasing prominence in synthetic and medicinal chemistry. In particular, bicyclo[2.1.1]hexanes (BCHs) been identified as the molecular replacement for benzenes. Here, we present facile access to a variety of BCHs via stepwise two-electron formal (3 + 2) cycloaddition between silyl enol ethers bicyclo[1.1.0]butanes (BCBs) under Lewis acid catalysis. The reaction features wide functional group tolerance ethers, allowing efficient construction two vicinal quaternary carbon centers silyl-protected tertiary alcohol unit streamlined fashion. Interestingly, with conjugated dienol can provide bicyclo[4.1.1]octanes (BCOs) equipped that facilitate further transformation. utilities this methodology are demonstrated by late-stage modification natural products, transformations units on bicyclo[2.1.1]hexane frameworks, derivatization bicyclo[4.1.1]octanes, delivering functionalized bicycles traditionally inaccessible.

Language: Английский

Citations

19
Enantioselective photocatalytic synthesis of bicyclo[2.1.1]hexanes as ortho-disubstituted benzene bioisosteres with improved biological activity DOI
Pablo Garrido-García, Irene Quirós, Paula Milán-Rois

et al.

Nature Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 25, 2025

Language: Английский

Citations

5
Pyridine-boryl radical-catalyzed [3π + 2σ] cycloaddition for the synthesis of pyridine isosteres DOI
Yuan Liu,

Shuang Lin,

Zhengwei Ding

et al.

Chem, Journal Year: 2024, Volume and Issue: unknown

Published: Sept. 1, 2024

Language: Английский

Citations

14
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 International Edition, Journal Year: 2024, Volume and Issue: 63(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

11
Facile Synthesis of Housanes by an Unexpected Strategy DOI
Yanyao Liu,

Somanea Tranin,

Yu‐Che Chang

et al.

Journal of the American Chemical Society, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 17, 2025

Rigid bicyclic hydrocarbons have emerged as important building blocks in the drug discovery industry. Despite progress this general area, bicyclo[2.1.0]pentanes (housanes) are an understudied class of molecules. Herein we report unconventional synthesis borylated housanes. Our method features a broad scope and high diastereoselectivities versatile intermediates. The route involves strain-release diboration bicyclo[1.1.0]butane intramolecular deborylative alkylation. versatility bridgehead boronic ester was demonstrated several functionalizations. Lastly, mechanism reaction investigated, unusual stereospecific diastereoselective ring expansion uncovered.

Language: Английский

Citations

2
Enantioselective [2π + 2σ] cycloaddition of bicyclobutanes with imines: An efficient approach to chiral 2-aza-bicyclo[2.1.1]hexanes DOI

Xuan-Ge Zhang,

Junjia Chen,

Zi-Yang Zhou

et al.

Chem Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 101295 - 101295

Published: March 1, 2025

Language: Английский

Citations

2
Borylated strain rings synthesis via photorearrangements enabled by energy transfer catalysis DOI Creative Commons
Shu-sheng Chen, Yu Zheng,

Zhi-Xi Xing

et al.

Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)

Published: April 19, 2025

Language: Английский

Citations

1