Catalytic Enantioselective Synthesis of Boron‐Stereogenic and Axially Chiral BODIPYs via Rhodium(II)‐Catalyzed C‐H (Hetero)Arylation with Diazonaphthoquinones and Diazoindenines DOI
Yankun Gao, Zizhen Liu, Sichao Tian

et al.

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

Published: Oct. 29, 2024

Abstract The molecular engineering of boron dipyrromethenes (BODIPYs) has garnered widespread attention due to their structural diversity enabling tailored physicochemical properties for optimal applications. However, catalytic enantioselective synthesis structurally diverse boron‐stereogenic BODIPYs through intermolecular desymmetrization and with atroposelectivity remains elusive. Here, we showcase rhodium(II)‐catalyzed site‐specific C−H (hetero)arylations prochiral polysubstituted diazonaphthoquinonesand diazoindenines, providing efficient pathways the rapid assembly versatile (hetero)arylated axially chiral long‐range axial rotational restriction modes. synthetic application procedures been emphasized by BODIPY derivatives various functions. Photophysical properties, bioimaging, lipid droplet‐specific targeting capability are also demonstrated, indicating promising applications in biomedical research, medicinal chemistry, material science.

Language: Английский

Catalytic asymmetric C–N cross-coupling towards boron-stereogenic 3-amino-BODIPYs DOI Creative Commons
Baoquan Zhan, Li‐Qing Ren,

Jiayi Zhao

et al.

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

Published: Jan. 7, 2025

3-Amino boron dipyrromethenes (BODIPYs) are a versatile class of fluorophores widely utilized in live cell imaging, photodynamic therapy, and fluorescent materials science. Despite the growing demand for optically active BODIPYs, synthesis chiral 3-amino-BODIPYs, particularly catalytic asymmetric version, remains challenge. Herein, we report boron-stereogenic 3-amino-BODIPYs via palladium-catalyzed desymmetric C–N cross-coupling prochiral 3,5-dihalogen-BODIPYs. This approach features broad substrate scope, excellent functional group tolerance, high efficiency, remarkable enantioselectivities, under mild reaction conditions. Further stereospecific formation 3,5-diamino-BODIPYs, along with an investigation into photophysical properties resulting optical BODIPYs also explored. protocol not only enriches chemical space chiroptical BODIPY dyes but contributes to realm chemistry. (BODIPYs), which useful science, authors first cross-couplings.

Language: Английский

Citations

7
Unlocking Diverse π-Bond Enrichment Frameworks by the Synthesis and Conversion of Boronated Phenyldiethynylethylenes DOI

Jinhui Xie,

Wangyang Li, Yong Lu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(14), P. 10167 - 10176

Published: March 27, 2024

The π-bond enrichment frameworks not only serve as a crucial building block in organic synthesis but also assume pivotal role the fields of materials science, biomedicine, photochemistry, and other related disciplines owing to their distinctive structural characteristics. incorporation various substituents into C═C double bonds tetrasubstituted alkenes is currently highly significant research area. However, with diverse on poses challenge achieving stereoselectivity. Here, we reported an efficient convergent route Cu-catalyzed borylalkynylation both symmetrical unsymmetrical 1,3-diynes, B2pin2, acetylene bromide construction boronated phenyldiethynylethylene (BPDEE) derivatives excellent chemo-, stereo-, regioselectivities. BPDEE could transform novel π-conjugated gem-diphenyldiethynylethylene (DPDEE), vinylphenyldiethynylethylene (VPDEE), phenyltriethynylethylene (PTEE) by stepwise process, which provides flexible platform for complex that were difficult synthesize previous methods. initial optical characterization revealed synthesized molecules exhibited aggregation-induced emission (AIE) properties, further establishes groundwork future applications enriches advances field functional research.

Language: Английский

Citations

15
Modular enantioselective assembly of multi-substituted boron-stereogenic BODIPYs DOI
Li‐Qing Ren, Baoquan Zhan,

Jiayi Zhao

et al.

Nature Chemistry, Journal Year: 2024, Volume and Issue: 17(1), P. 83 - 91

Published: Sept. 20, 2024

Language: Английский

Citations

14
Boron‐Stereogenic Compounds: Synthetic Developments and Opportunities DOI

Yonghong Guo,

Bing Zu,

C. Chen

et al.

Chinese Journal of Chemistry, Journal Year: 2024, Volume and Issue: 42(19), P. 2401 - 2411

Published: May 27, 2024

Comprehensive Summary The 21 st century has witnessed a continuous evolution in the development of boron‐stereogenic chemistry. Since 1990s, various innovations for synthesis tetracoordinate compounds, which exhibited great potential applications, have been demonstrated by synthetic chemists. This paper reviews significant progress and recent advances towards assembly enantioenriched hopes to shed light on new perspectives inspire further research this emerging field.

Language: Английский

Citations

9
Catalytic Enantioselective Synthesis of Boron‐Stereogenic and Axially Chiral BODIPYs via Rhodium(II)‐Catalyzed C‐H (Hetero)Arylation with Diazonaphthoquinones and Diazoindenines DOI
Yankun Gao, Zizhen Liu, Sichao Tian

et al.

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

Published: Oct. 29, 2024

The molecular engineering of boron dipyrromethenes (BODIPYs) has garnered widespread attention due to their structural diversity enabling tailored physicochemical properties for optimal applications. However, catalytic enantioselective synthesis structurally diverse boron-stereogenic BODIPYs through intermolecular desymmetrization and with atroposelectivity remains elusive. Here, we showcase rhodium(II)-catalyzed site-specific C-H (hetero)arylations prochiral polysubstituted diazonaphthoquinonesand diazoindenines, providing efficient pathways the rapid assembly versatile (hetero)arylated axially chiral long-range axial rotational restriction modes. synthetic application procedures been emphasized by BODIPY derivatives various functions. Photophysical properties, bioimaging, lipid droplet-specific targeting capability are also demonstrated, indicating promising applications in biomedical research, medicinal chemistry, material science.

Language: Английский

Citations

7
Catalytic insertion of nitrenes into B-H bonds DOI Creative Commons
Nikita M. Ankudinov, Nikita V. Alexeev, Evgeniya Podyacheva

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

Catalytic insertion of nitrenes into B–H bonds produces unique compounds with chiral boron atoms.

Language: Английский

Citations

1
Cu-Catalyzed Enantioselective Carbene Insertion into Ge–H and Si–H Bonds Enabled by SPSiBox with a Tunable Chiral Pocket DOI
Shihao Chen,

Sheng-Ye Zhang,

Ziyang Chen

et al.

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

Published: April 28, 2025

Here, we report the Cu-catalyzed asymmetric carbene insertion into both Ge-H and Si-H bonds with α-trifluoromethyl diazo compounds, enabled by a class of newly developed C2-symmetrical bisoxazoline ligands. This protocol provides an efficient method for preparation enantioenriched ogranogermanes organosilanes, featuring broad substrate scope, mild reaction conditions, excellent enantioselectivity, low catalyst loading. The key to tolerance is use SPSiBox ligands bearing flexible tunable chiral pocket. Preliminary mechanistic studies computational unveiled origin induction ligands, mechanism insertion. not only new construction trifluoromethyl-containing molecules but also opens avenue Si- Ge-containing functional molecules.

Language: Английский

Citations

1
Accessing Functionalized Furans from Reacting Enynones and Enynals through Furyl Metal Carbenes DOI

Ho‐Jun Cho,

Ju Hyun Kim

Asian Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 13(4)

Published: Jan. 3, 2024

Abstract Enynones and enynals represent donor‐type carbene precursors that efficiently form furyl metal carbenes via a catalytic intramolecular 5‐exo‐dig cyclization rearrangement cascade, in 100 % atom‐economical manner, using various metals. These have been successfully utilized numerous reactions, including X−H insertion, cyclopropanations, metathesis, cross‐coupling, demonstrating broad reaction scope efficiency constructing highly functionalized furans. Recent years witnessed significant advancements transformations involving carbenes, especially asymmetric insertion domino reactions zwitterionic intermediates, strategies, their application synthesizing functional materials drug candidates. In this review, we summarize recent progress generated from enynones enynals, focusing on the synthesis of

Language: Английский

Citations

4
Cu-catalyzed enantioselective assembly of axially chiral allylic boronates DOI
Shuai Wang, Jianbo Liu,

Wenyue Ma

et al.

Science China Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 25, 2024

Language: Английский

Citations

4
Supramolecular‐Assembly and Surfactant‐Regulated Circularly Polarized Luminescence from a Spiranic BINOL‐Derived Borate Isoindolyl‐Indolenine (BBI) Dye DOI

Yingzhu Sun,

Changjiang Yu, Tingting Yu

et al.

Advanced Optical Materials, Journal Year: 2025, Volume and Issue: unknown

Published: April 4, 2025

Abstract Circularly polarized luminescence (CPL) materials have attracted significant attention owing to their unique luminescent properties and broad range of applications. However, challenges remain, including controlling helical assembly, mitigating aggregation‐caused quenching, balancing quantum yield ( Φ PL ) with g values. Here, the study reports synthesis a novel asymmetric, spiranic O‐organoboranes bearing isoindolyl‐indolenine scaffold (BBI) axial chirality through BINOL substitution, as well its supramolecular assembly surfactant‐regulated tunable CPL behaviors. The newly designed BBI dye shows relative weak 10% in toluene. Supramolecular acetonitrile/water co‐solvents exhibit an obvious aggregation‐induced emission (AIE) process, leading formation spherical nanostructures red‐shifted orange‐yellow (554 nm, = 0.012, 7%). Moreover, surfactant sodium dodecyl sulfonate (SDS) can promote aggregation pure deionized water, producing nanofibers blue‐shifted yellow (536 0.006, 13%). Crystal growth toluene/hexane SDS aqueous/acetonitrile systems reveals chiral crystals P 212121 space group, offering insights into amplification. This demonstrates ability precisely control parameters, X‐ray single‐crystal analysis providing additional understanding regulation.

Language: Английский

Citations

0