Electricity‐Driven Strain‐Release Cascade Cyclization of Bicyclo[1.1.0]butane (BCB): Stereoselective Synthesis of Functionalized Spirocyclobutyl Oxindoles DOI
Rajib Maity, Satya Paul, Ankita Sen

et al.

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

Published: Oct. 23, 2024

Abstract Spirocyclobutyl oxindoles, characterized by their unique three‐dimensional structures, are valuable building blocks for many pharmacophores and drug units. However, stereoselective synthetic strategies these scaffolds remain underdeveloped, with most existing methods relying on transition metal catalysts stoichiometric redox reagents. In this work, we introduce an electrochemical strain‐release driven cascade spirocyclization of bicyclo[1.1.0]butane (BCB) derivatives the synthesis functionalized spirocyclobutyl oxindoles. Tetrabutylammonium bromide serves a dual purpose as both supporting electrolyte brominating agent. The method offers broad substrate scope, high atom economy, excellent diastereoselectivity. stereoselectivity product is controlled minimizing dipolar repulsion between amide C=O C−Br bonds. We also explored methodology′s versatility applying it to various functionalizations demonstrated its scalability practical use. efficient derivatization products allowed rapid creation diverse library

Language: Английский

Strain-release transformations of bicyclo[1.1.0]butanes and [1.1.1]propellanes DOI Creative Commons
Qianqian Hu, Jie Chen, Yang Yang

et al.

Tetrahedron Chem, Journal Year: 2024, Volume and Issue: 9, P. 100070 - 100070

Published: Feb. 28, 2024

Bicyclo[1.1.0]butanes (BCBs) and [1.1.1]propellanes (tricyclo[1.1.1.01,3]pentanes, TCPs) are structurally unique compounds with different chemical properties. Strain-release driven reactions have emerged as an atom- step-economic strategy for the organic synthesis. Using this strategy, a variety of functional ring molecules been efficiently synthesized, including various cyclobutane molecules, bicyclo[2.1.1]hexanes, bicyclo[1.1.1]pentanes, others. More specifically, these strain release-driven include aspects nucleophilic addition, radical electrophilic or transition metal catalysis. This review will discuss recent developments in strain-release transformations bicyclo[1.1.0]butanes [1.1.1]propellanes.

Language: Английский

Citations

26
Lewis acid-catalyzed diastereoselective formal ene reaction of thioindolinones/thiolactams with bicyclobutanes DOI Creative Commons
Avishek Guin,

Shiksha Deswal,

Mahesh Singh Harariya

et al.

Chemical Science, Journal Year: 2024, Volume and Issue: 15(31), P. 12473 - 12479

Published: Jan. 1, 2024

Bicyclo[1.1.0]butanes (BCBs), featuring two fused cyclopropane rings, have found widespread application in organic synthesis. Their versatile reactivity towards radicals, nucleophiles, cations, and carbenes makes them suitable for various reactions, including ring-opening annulation strategies. Despite this versatility, their potential as enophiles an ene reaction remains underexplored. Considering given the challenges of achieving diastereoselectivity reactions BCBs, herein, we present a unique method utilizing BCBs mild diastereoselective Sc(OTf)

Language: Английский

Citations

12
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

11
Synthesis of Cyclobutanes and Cyclobutenes by Strain-Release-Driven Ring-Opening of Bicyclo[1.1.0]butanes DOI

Xuan Zhan,

Heng-Xian He,

Quanxin Peng

et al.

Synthesis, Journal Year: 2024, Volume and Issue: 56(24), P. 3829 - 3848

Published: Aug. 23, 2024

Abstract Cyclobutanes and cyclobutenes exhibit intriguing structures demonstrate significant biological activities diverse synthetic applications. This review aims to summarize recent progress in strain-release-driven ring-opening reactions of bicyclo[1.1.0]butanes (BCBs) synthesize these four-membered carbon rings. It outlines the strategies, regio- stereoselectivity, scope reactions, mechanistic implications catalytic process, providing a supplementary perspective existing reviews. 1 Introduction 2 Thermally Driven Nucleophilic Ring-Opening 3 Rearrangement Isomerization Reaction 4 Light-Driven 5 Transition-Metal/Lewis Acid Catalyzed 6 Conclusion Outlook

Language: Английский

Citations

7
Pyridine-Boryl Radical-Catalyzed [3π + 2σ] Cycloaddition for the Synthesis of Pyridine Bioisosteres DOI Creative Commons
Honggen Wang, Yuan Liu,

Shuang Lin

et al.

Published: April 1, 2024

The exploration of C(sp3)-rich three-dimensional (3D) scaffolds as bioisosteres for planar aromatics has garnered increasing attention. While the bioisosterism benzenes been extensively studied, pyridines, second most prevalent aromatic compounds in pharmaceuticals, faces additional challenges and encountered surprisingly limited success. In this study, we propose unprecedented 2-azabicyclo[3.1.1]heptenes effective 1,3,5-trisubstituted pyridines terms not only 3D conformation but also basicity. We develop a pyridine-boryl radical-catalyzed [3π + 2σ] cycloaddition reaction vinyl azides with bicyclo[1.1.0]butanes (BCBs) an efficient synthetic approach. Synthetic manipulation products reveals valuable handles, allowing modular synthesis various pyridine bioisosteres.

Language: Английский

Citations

6
Visible-light-mediated substituent-controlled regiodivergent (2 + 2)/(3 + 2) cycloadditions for the synthesis of aza-analogs of β-lactam and γ-fused lactam derivatives DOI

Wei‐Fang Zuo,

Yang Zhang,

Yulin Luo

et al.

Organic Chemistry Frontiers, Journal Year: 2024, Volume and Issue: 11(13), P. 3576 - 3582

Published: Jan. 1, 2024

Substituent-controlled regiodivergent synthesis of aza-analogs β-lactam and γ-fused lactam derivatives via the visible-light-induced Wolff rearrangement α-diazoketones azo esters.

Language: Английский

Citations

4
Photoredox-Catalyzed Strain-Release-Driven Synthesis of Functionalized Spirocyclobutyl Oxindoles DOI
Tushar Singha, Nakul Abhay Bapat, Subrat Kumar Mishra

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(30), P. 6396 - 6401

Published: July 24, 2024

Spirocyclobutyl oxindoles have garnered substantial attention in drug discovery and pharmaceuticals owing to their wide range of biological activities. Strain-release small-ring compounds is a powerful strategy enable efficient access complex molecules. In this study, we successfully realized photoredox-catalyzed strain-release radical spirocyclization approach attain functionalized spirocyclobutyl oxindoles. A diverse array radicals, such as sulfonyl, phosphonyl, trifluoromethyl, were added efficiently the strained C-C σ-bond bicyclobutanes (BCBs) afford library Furthermore, obtained products could be transformed into valuable building blocks. The observed reactivity selectivity been rationalized based on density functional theory calculations.

Language: Английский

Citations

4
Recent Progress in Visible Light‐Mediated Synthesis of γ‐lactams DOI Open Access
Suman Pradhan, Shoubhik Das

Helvetica Chimica Acta, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 30, 2025

Abstract The integration of sustainable practices, such as employing renewable light sources for synthesizing valuable synthetic scaffolds, has been progressing over the past few decades. Among these noteworthy organic frameworks, lactams, particularly γ‐lactams, have established their prominence due to extensive applications in pharmaceutical, agricultural, and medicinal domains. This growing significance γ‐lactams spurred considerable interest synthesis, especially via milder, more sustainable, environmentally friendly methods. In recent years, numerous innovative reaction mechanisms explored, highlighting how photocatalysis can enable formation from readily accessible precursors through C−N bond cyclization processes. review emphasizes potential photocatalytic strategies not only enhance current methods but also foster development greener chemical processes future.

Language: Английский

Citations

0
Copper-Catalyzed Cross-Coupling of Bicyclobutanes with Triftosylhydrazone Leading to Skipped Dienes DOI
Xiaolong Zhang, Tian Tian, Xiwei Qi

et al.

Organic Letters, Journal Year: 2025, Volume and Issue: unknown

Published: March 4, 2025

Here, we report a protocol for the synthesis of skipped dienes through cross-coupling bicyclo[1.1.0]butanes with trifluoromethyl triftosylhydrazones. The reaction is run using TpBr3Cu(NCMe) as catalyst to give access library trifluoromethylated (32 examples, ≤98% yield) excellent E/Z selectivity under mild and operationally safe conditions. presented methods proved be compatible various functionalized

Language: Английский

Citations

0
Rhodium(II)-Catalyzed Strain-Enabled Stereoselective Synthesis of Skipped Dienes DOI
Ganesh Arjun Kadam, Tushar Singha,

Sapna Rawat

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(16), P. 12225 - 12233

Published: Aug. 1, 2024

Skipped dienes are not only present in fatty acid primary metabolites and natural products but also serve as reactive intermediates diverse chemical synthesis. Despite this, the regioselective stereoselective synthesis of skipped remains a challenging goal. Strain release organic molecules is powerful tool for creating complexity under mild conditions. The reactivity strained bicyclo[1.1.0]butane (BCB) systems mainly dominated by transformations relying on their innate electrophilic reactivity. Herein, we report rare example carbene-type BCB system based rhodium–carbene chemistry, which enables highly through strain release. reaction compatible with range functional groups both diazo compounds BCBs could be applied successfully to complex structures, providing valuable functionalizable dienes. introduced during served synthetic handles downstream manipulations. high stereoselectivity observed has been rationalized DFT calculations, suggests that likely proceeding via concerted mechanism, noncovalent interactions between metallocarbene control exclusive selectivity.

Language: Английский

Citations

2