Convenient partial reduction of CO2 to a useful C1 building block: efficient access to 13C‐labelled N‐heterocyclic carbenes DOI Creative Commons

Nicholas A. Phillips,

Joshua S. Sapsford,

Dániel Csókás

et al.

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

Published: Oct. 8, 2024

Abstract The selective, transition metal‐free hydrosilylation of CO 2 to CH (OSiEt 3 ) has been achieved under mild conditions and in high isolated yields (up 90%) by using Et SiH the simple, easily prepared borohydride catalyst Li + [HB(C 6 F 5 ] − . resulting ‐derived bis(silyl)acetal product—whose mechanism formation interrogated through detailed computational experimental studies—can be rapidly valorized facile synthesis N ‐heterocyclic carbenes, via their corresponding imidazolium salts. By relatively inexpensive, isotopically enriched 13 this protocol can exploited prepare NHC isotopologues that are selectively C labelled at key, ligating C2 position. This provides an electronically responsive NMR spectroscopic handle with dramatically enhanced sensitivity, which directly benefit reactivity studies both organo‐ organometallic catalysis, where use is ubiquitous.

Language: Английский

Selective Conversions of CO2 into Value-Added Chemicals via Cooperative Catalysis Using Multifunctional Catalysts DOI
Tadashi Ema

Bulletin of the Chemical Society of Japan, Journal Year: 2023, Volume and Issue: 96(7), P. 693 - 701

Published: June 8, 2023

Abstract Carbon dioxide (CO2) is not only a greenhouse gas but also renewable carbon source for organic synthesis. Here we have summarized our studies on the conversions of CO2 into value-added chemicals via cooperative catalysis using multifunctional catalysts. For example, bifunctional metalloporphyrin catalysts with quaternary ammonium halides were developed selective synthesis cyclic carbonates or polycarbonates from epoxides and CO2. Bifunctional MgII ZnII porphyrins showed high catalytic activity carbonates, while AlIII catalyzed copolymerization cyclohexene oxide to give poly(cyclohexene carbonate). The activities resulted action central metal ion salts. Chiral kinetic resolution terminal internal developed. In addition, macrocyclic multinuclear complex Zn5L3, which was synthesized by self-assembly Zn(OAc)2 BINOL derivative (L), reduction phenylsilane produce various useful synthetic intermediates compounds.

Language: Английский

Citations

18
Skeletal Formation of Carbocycles with CO2: Selective Synthesis of Indolo[3,2-b]carbazoles or Cyclophanes from Indoles, CO2, and Phenylsilane DOI
Sha Li,

S. NAKAHARA,

Taishin Adachi

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(22), P. 14935 - 14941

Published: May 9, 2024

The catalytic reactions of indoles with CO2 and phenylsilane afforded indolo[3,2-b]carbazoles, where the fused benzene ring was constructed by forming two C–H bonds four C–C molecules via deoxygenative conversions. Nine-membered cyclophanes made up three were also obtained, cyclophane framework six bonds. These multicomponent cascade giving completely different carbocycles switched simply choosing solvent, acetonitrile or ethyl acetate.

Language: Английский

Citations

4
Diastereoselective Formal [3+3] Cascade Cyclization towards Fused 4‐Fluoroalkylated 3,4‐Dihydro‐2H‐pyrans via Copper Catalysis DOI

Weigao Hu,

Jiawen Yin,

Zhiyong Li

et al.

Chinese Journal of Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: April 25, 2025

Comprehensive Summary The cycloaddition and annulation reactions offer a powerful method toward various important substituted 3,4‐dihydro‐2 H ‐pyran architectures. Nevertheless, the transformation for preparing fused‐polycyclic ones still remains challenging yet highly desirable until now. Herein, we report novel formal [3+3] cascade cyclization reaction to provide lactam‐fused 4‐fluoroalkylated 3,4‐dihydropyran skeletons bearing three contiguous tertiary carbon centers via copper catalysis. Of note, these annulations proceeded in an exclusively diastereoselective manner through successive inert C(sp 2 )‐Cl 3 )‐H functionalization, which exhibited site‐selectivity stereoselectivity. Additionally, evaluations on biological activities of obtained products revealed that several display inhibitory activity against Siha H1975 cancer cell lines.

Language: Английский

Citations

0
Bimolecular reduction of carbon dioxide: double synthons for alkynes trifunctionalization DOI
Wenfang Xiong,

Xiaobin Tan,

Hongjian Liu

et al.

Science China Chemistry, Journal Year: 2023, Volume and Issue: 67(3), P. 841 - 847

Published: Dec. 14, 2023

Language: Английский

Citations

3
Six-membered ring systems: With O and/or S atoms DOI
Clementina M.M. Santos, Artur M. S. Silva

Progress in heterocyclic chemistry, Journal Year: 2024, Volume and Issue: unknown, P. 421 - 484

Published: Jan. 1, 2024

Language: Английский

Citations

0
Convenient partial reduction of CO2 to a useful C1 building block: efficient access to 13C‐labelled N‐heterocyclic carbenes DOI Creative Commons

Nicholas A. Phillips,

Joshua S. Sapsford,

Dániel Csókás

et al.

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

Published: Oct. 8, 2024

Abstract The selective, transition metal‐free hydrosilylation of CO 2 to CH (OSiEt 3 ) has been achieved under mild conditions and in high isolated yields (up 90%) by using Et SiH the simple, easily prepared borohydride catalyst Li + [HB(C 6 F 5 ] − . resulting ‐derived bis(silyl)acetal product—whose mechanism formation interrogated through detailed computational experimental studies—can be rapidly valorized facile synthesis N ‐heterocyclic carbenes, via their corresponding imidazolium salts. By relatively inexpensive, isotopically enriched 13 this protocol can exploited prepare NHC isotopologues that are selectively C labelled at key, ligating C2 position. This provides an electronically responsive NMR spectroscopic handle with dramatically enhanced sensitivity, which directly benefit reactivity studies both organo‐ organometallic catalysis, where use is ubiquitous.

Language: Английский

Citations

0