Stereoselective C−B and C−H Bonds Functionalization of PolyBorylated Alkenes DOI Creative Commons

Narendra Kumar Vaishanv,

Nadim Eghbarieh, Rahul A. Jagtap

et al.

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

P-Stereogenic Phosphorus Ligands in Asymmetric Catalysis DOI
Tsuneo Imamoto

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(14), P. 8657 - 8739

Published: July 2, 2024

Chiral phosphorus ligands play a crucial role in asymmetric catalysis for the efficient synthesis of useful optically active compounds. They are largely categorized into two classes: backbone chirality and P-stereogenic ligands. Most reported belong to former class. Privileged ones such as BINAP DuPhos frequently employed wide range catalytic transformations. In contrast, latter class has remained small family many years mainly because their synthetic difficulty. The late 1990s saw emergence novel with superior enantioinduction ability Rh-catalyzed hydrogenation reactions. Since then, numerous have been synthesized used This Review summarizes thus far, including stereochemical electronic properties that afford high excellent enantioselectivities. Examples reactions use this described together applications construction key intermediates natural products therapeutic agents. literature covered dates back 1968 up until December 2023, centering on studies published later years.

Language: Английский

Citations

41
Enantioselective Copper-Catalyzed Ring-Opening Diboration of Arylidenecyclopropanes to Access Chiral Skipped 1,4- and 1,3-Diboronates DOI
Wenrui Zheng,

Boon Beng Tan,

Shaozhong Ge

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(8), P. 5366 - 5374

Published: Feb. 14, 2024

Two enantioselective approaches to synthesize chiral skipped diboronate compounds have been developed, relying on copper-catalyzed one-pot asymmetric ring-opening diboration of arylidenecyclopropanes. A wide range arylidenecyclopropanes react smoothly with HBpin in the presence CuOAc and (R)-DTBM-Segphos, affording 1,4-diboronates high enantioselectivity (up 99% ee). Meanwhile, a variety selectively B2pin2 (S,S)-Ph-BPE sequential addition MeOH, providing 1,3-diboronates 98% These enantioenriched 1,3- can undergo various enantiospecific transformations minimal loss their enantiopurity. Mechanistic studies reveal that these two processes start CuH-catalyzed hydroboration form mixture Z/E-homoallyl boronate intermediates, which subsequently second or Cu-Bpin-catalyzed protoboration produce 1,3-diboronates, respectively.

Language: Английский

Citations

18
Developing Biarylhemiboronic Esters for Biaryl Atropisomer Synthesis via Dynamic Kinetic Atroposelective Suzuki–Miyaura Cross-Coupling DOI

Yiming Yang,

Changhui Wu,

Junhao Xing

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(9), P. 6283 - 6293

Published: Feb. 21, 2024

We herein introduce biarylhemiboronic esters as a new type of bridged biaryl reagent for asymmetric synthesis axially chiral structures, and the palladium-catalyzed Suzuki-Miyaura cross-coupling is developed. This dynamic kinetic atroposelective coupling reaction exhibits high enantioselectivity, good functional group tolerance, broad substrate scope. The synthetic application current method was demonstrated by transformations product programmed polyarene. Preliminary mechanistic studies suggested that proceeded via an enantio-determining transmetalation step.

Language: Английский

Citations

16
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

10
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

9
Amino Acid-Derived Ionic Chiral Catalysts Enable Desymmetrizing Cross-Coupling to Remote Acyclic Quaternary Stereocenters DOI Creative Commons
Junqiang Wei, Vincent Gandon, Ye Zhu

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(30), P. 16796 - 16811

Published: July 20, 2023

Synthetic application of asymmetric catalysis relies on strategic alignment bond construction to creation chirality a target molecule. Remote desymmetrization offers distinctive advantages spatial decoupling catalytic transformation and generation stereogenic element. However, such separation presents substantial difficulties for the chiral catalyst discriminate distant enantiotopic sites through reaction three or more bonds away from prochirality center. Here, we report strategy that establishes acyclic quaternary carbon stereocenters cross-coupling reactions at distal positions aryl substituents. The new class amino acid-derived ionic catalysts enables desymmetrizing (enantiotopic-group-selective) Suzuki-Miyaura reaction, Sonogashira Buchwald-Hartwig amination between diverse diarylmethane scaffolds aryl, alkynyl, coupling partners, providing rapid access enantioenriched molecules project substituents widely spaced in three-dimensional space. Experimental computational investigations reveal electrostatic steering substrates by C-terminus ligands interactions. Cooperative ion-dipole interactions catalyst's amide group potassium cation aid preorganization transmits asymmetry product. This study demonstrates it is practical achieve precise long-range stereocontrol engineering arrangements catalysts' substrate-recognizing groups metal centers.

Language: Английский

Citations

18
Ligand-Exchange-Enabled Axially Chiral Recognition in Asymmetric Aminopalladation/Olefination of 2-Alkynylanilides DOI
Gang Wang, Ni Zhang,

Bing‐Xia Yan

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(6), P. 4053 - 4065

Published: March 1, 2024

Chiral recognition for the synthesis of axially chiral biaryl units is a fundamental and challenging topic in organic synthesis. Herein, we documented that an efficient O-ligand exchange between catalyst substrate enabled axial asymmetric aminopalladation/olefination 2-alkynylanilides vinyl trifluoromethanesulfonates, providing 3-alkenylindoles with up to 97% ee 98% yield. This protocol features mild conditions, broad functional group tolerance, scalability, late-stage modification bioactive molecules. Experimental computational studies hinted (R)-BIDIME/Pd complex alkoxy was crucial success stereoselectivity control.

Language: Английский

Citations

6
Catalysis and Synthesis Enabled by P-Chiral Dihydrobenzooxaphosphole Ligands DOI
Zhen Cao, Dongyang He, Wenjun Tang

et al.

Organic Process Research & Development, Journal Year: 2024, Volume and Issue: 28(4), P. 949 - 977

Published: April 8, 2024

P-Chiral phosphorus ligands received little attention in organic chemistry until Knowles made his landmark contribution asymmetric hydrogenation by developing the P-chiral CAMP and DIPAMP. The development of accelerated end last century with advent some highly efficient renowned for hydrogenation, including BisP*, TangPhos, QuinoxP*, DuanPhos, et al. However, most reported were air-sensitive, difficult to make, or lacked structural modularity, hampering their availability applicability. sterically electronically tunable is particularly desirable. Over past decade, a family hindered, electron-rich, structurally tunable, air-stable dihydrobenzooxaphosphole emerged that proved be versatile various transformations. 5 years witnessed an increasing number studies related these discovery unprecedented catalytic properties This review highlights unique catalysis applications synthesis natural products therapeutic agents.

Language: Английский

Citations

5
Palladium-Catalyzed Enantioselective Stereodivergent Desymmetrization of Cyclic 1,4-Allyldiboronates DOI
Hao Liang, Lorenzo D. Battistoni,

Sergei Tcyrulnikov

et al.

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

Published: Feb. 4, 2025

In the presence of a chiral palladium-based catalyst, 1,4-diboryl-2-alkenes undergo enantioselective cross-coupling that results in desymmetrization substrate structure. Depending on reaction conditions and choice ligand, can occur with cis or trans selectivity, allowing construction an array different substituted carbocycles enantiomerically enriched fashion.

Language: Английский

Citations

0
Palladium nanoparticles from β-cyclodextrin and cellulose methyl carboxylate as an effective catalyst for Sonogashira coupling and the reduction of alkynes DOI Creative Commons
Van‐Dung Le, Thi‐Kim‐Chi Huynh, Van‐Duong Dao

et al.

RSC Advances, Journal Year: 2025, Volume and Issue: 15(14), P. 10534 - 10546

Published: Jan. 1, 2025

This study presents a novel PdNPs@β-CD-CMC catalyst synthesized from β-CD and CMC, in which basic medium can reduce Pd 2+ to PdNPs, while CMC acts as an effective cost-efficient support.

Language: Английский

Citations

0