Organic Letters, Journal Year: 2024, Volume and Issue: unknown
Published: Nov. 24, 2024
We report a new and straightforward route toward substituted benzo[
Language: Английский
Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(14), P. 10142 - 10149
Published: March 27, 2024
Saturated bicyclic compounds make up a valuable class of building blocks in the development agrochemicals and pharmaceuticals. Here, we present synthesis borylated bicyclo[2.1.1]hexanes via crossed [2 + 2]-cycloaddition. Due to presence C–B bond, variety structures can be easily prepared that are not accessible by other methods. Moreover, rare photo-ene reaction is also disclosed, allowing for diastereoselective trisubstituted cyclopentanes.
Language: Английский
Citations
28
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
Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: unknown
Published: Sept. 26, 2024
Language: Английский
Citations
5
The Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: unknown
Published: March 19, 2025
Multi(boronate) esters are useful building blocks in modern chemical synthesis. Herein, we have developed an efficient, transition metal- and solvent-free method for the regioselective boration of alkenes alkynes. The alkali metal Lewis base (NaOMe)-mediated reactions, using bis(pinacolato)diboron (B2pin2) as boron reagent, resulted diboration at room temperature triboration alkynes 60 °C to produce synthetically alkyl 1,2-bis(boronate) 1,1,2-tris(boronate) esters, respectively, excellent yields with high regioselectivity. This environmentally benign protocol demonstrates a broad substrate scope good functional group tolerance gram-scale reaction further highlights practical usefulness method. proposed pathway has been evaluated based on stoichiometric reactions DFT studies.
Language: Английский
Citations
0
Organic Letters, Journal Year: 2025, Volume and Issue: unknown
Published: April 11, 2025
Herein, we disclose a manganese-catalyzed approach that enables the direct iododiborylcarbofunctionalization of alkynes with (diboronmethyl)iodide under mild conditions. This grants access to range structurally unique and synthetically useful γ-iodine-substituted gem-bis(boronate)s, which have hitherto been inaccessible. atom-economical strategy displays excellent functional-group tolerance, encompasses wide applicable substrates, demonstrates high Z:E selectivity (up 96:4).
Language: Английский
Citations
0
Nature Communications, Journal Year: 2025, Volume and Issue: 16(1)
Published: April 19, 2025
Language: Английский
Citations
0
Beilstein Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 21, P. 854 - 863
Published: April 30, 2025
The photoactivation of organic molecules via energy transfer (EnT) catalysis is often limited to conjugated systems that have low-energy triplet excited states, with simple alkenes remaining an intractable challenge. ability address this limitation, using high sensitizers, would represent attractive platform for future reaction design. Here, we disclose the alkenylboronic esters established alkene scrambling as a rapid probe identify suitable catalyst and boron motif. Cyclic voltammetry, UV–vis analysis, control reactions support sensitization, enabling intramolecular [2 + 2] cycloaddition be realized accessing 3D bicyclic fragments containing handle.
Language: Английский
Citations
0
Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(45)
Published: July 9, 2024
Abstract Alkenes are fundamental functional groups which feature in various materials and bioactive molecules; however, efficient divergent strategies for their stereodefined synthesis difficult. In this regard, numerous synthetic methodologies have been developed to construct carbon–carbon bonds with regio‐ stereoselectivity, enabling the predictable of alkenes. fact, an appealing alternative approach accessing challenging alkene molecular frameworks could involve sequential selective activation cross‐coupling strong instead conventional C−C bond formation. study, we introduce a series programmed site‐ stereoselective that capitalizes on versatile reactivity readily accessible polymetalloid alkenes (i.e. polyborylated alkenes), through tandem reaction, is catalyzed by organometallic Rh‐complex produce complex scaffolds. By merging C−B remote C−H functionalization, achieve situ generation polyfunctional C(sp 2 )‐nucleophilic intermediates. These species can be further modified coupling reactions C‐based electrophiles, formation )−C(sp 3 ) even more architectures using available starting polyborylated‐alkenes. Mechanistic computational studies provide insight into origins stereoselectivities via 1,4‐Rh migration process.
Language: Английский
Citations
1
Angewandte Chemie, Journal Year: 2024, Volume and Issue: 136(45)
Published: July 9, 2024
Abstract Alkenes are fundamental functional groups which feature in various materials and bioactive molecules; however, efficient divergent strategies for their stereodefined synthesis difficult. In this regard, numerous synthetic methodologies have been developed to construct carbon–carbon bonds with regio‐ stereoselectivity, enabling the predictable of alkenes. fact, an appealing alternative approach accessing challenging alkene molecular frameworks could involve sequential selective activation cross‐coupling strong instead conventional C−C bond formation. study, we introduce a series programmed site‐ stereoselective that capitalizes on versatile reactivity readily accessible polymetalloid alkenes (i.e. polyborylated alkenes), through tandem reaction, is catalyzed by organometallic Rh‐complex produce complex scaffolds. By merging C−B remote C−H functionalization, achieve situ generation polyfunctional C(sp 2 )‐nucleophilic intermediates. These species can be further modified coupling reactions C‐based electrophiles, formation )−C(sp 3 ) even more architectures using available starting polyborylated‐alkenes. Mechanistic computational studies provide insight into origins stereoselectivities via 1,4‐Rh migration process.
Language: Английский
Citations
0
Chemical Science, Journal Year: 2024, Volume and Issue: unknown
Published: Jan. 1, 2024
Heteroatom-substituted ethylenes have long been studied owing to their potential application electronic devices. In contrast well-studied π-donor substituted ethylene, the π-acceptor one has only limitedly reported. While boron can be a candidate of π-acceptors, there still no example fully conjugated tetraborylethylene (TBE). Herein, we synthesized first TBE 2 by selenium-mediated C-C double bond formation from diborylcarbenoid 1, synthetic equivalent diborylcarbene (DBC). An intermediate bis(diborylmethylene)-λ
Language: Английский
Citations
0