Nickel-Catalyzed 1,1-Carboboration of Polysubstituted Internal Alkenes DOI
Yao Tong, Shiyang Wang, Yu Liu

et al.

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

Published: April 1, 2025

Herein, we report a nickel-catalyzed 1,1-carboboration of di- and trisubstituted alkenyl boronates through chain-walking strategy. This reaction effectively addresses the polarity-mismatch problem via ligand control, enabling coupling various carbon-based electrophiles while accommodating broad range functional groups. The approach yields diverse tetrasubstituted carbon gem-diboronate derivatives with exceptional regioselectivity. synthetic utility this method is further demonstrated concise synthesis high-value bioactive molecules.

Language: Английский

Diverse Synthesis of C-Glycosides by Stereoselective Ni-Catalyzed Carboboration of Glycals DOI
Mao‐Yun Lyu, Samuel A. Jacobo, M. Kevin Brown

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(28), P. 18866 - 18872

Published: July 5, 2024

C-Glycosides are important structures that common to natural products and pharmaceutical agents. Established methods for their synthesis involve the reaction of an activated anomeric carbon. In this study, we report a conceptually new approach involves stereoselective Ni-catalyzed carboboration glycals. these reactions, not only is C–C bond formed at carbon, but synthetically useful C–B also installed. Upon oxidation, differentially protected C-glycosides be formed. addition, stereospecific manipulation leads diverse C-glycosides. Finally, application method in established C-glycosides, such as C-glycosyl amino acids, well strategy make all possible diastereomers C1 C2.

Language: Английский

Citations

10
Ni-Catalyzed Regioselective and Site-divergent Reductive Arylalkylations of Allylic Amines DOI Creative Commons
Huan Meng, Jun-Song Jia, Pengfei Yang

et al.

Chemical Science, Journal Year: 2025, Volume and Issue: 16(10), P. 4442 - 4449

Published: Jan. 1, 2025

Catalytic methods by switching the least parameters for regioselective and site-divergent transformations to construct different architectures from identical readily available starting materials are among most ideal catalytic protocols. However, associated challenge precisely control both regioselectivity site diversity renders this strategy appealing yet challenging. Herein, Ni-catalyzed cross-electrophile 1,2- 1,3-arylalkylations of N-acyl allylic amines have been developed. This reductive three-component protocol enables 1,2-arylalkylation 1,3-arylalkylation with aryl halides alkyl excellent chemo-, regio- site-selectivity, representing first example controlled migratory difunctionalization alkenes under conditions. A wide range terminal internal unactivated amines, precursors were tolerated, providing straightforward efficient access diverse C(sp3)-rich branched aliphatic materials.

Language: Английский

Citations

1
Palladium-catalyzed enantioselective β-hydride elimination for the construction of remote stereocenters DOI Creative Commons
Shaozi Sun, Shengnan Sun, Weiwei Zi

et al.

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

Published: March 5, 2025

The β-H elimination is a crucial elementary step in transition-metal catalysis, but controlling the stereochemistry of this process has been underdeveloped. limited works reported so far have only focused on creating axial chirality allenes, and no report able to build central using asymmetric elimination. In study, we Trost ligand-enabled enantioselective desymmetric reaction from π-allyl-Pd. This transformation provides rapid access cyclohexenes bearing C4-remoted stereocenter, total synthesis (-)-oleuropeic acid (-)-7-hydroxyterpineol demonstrated. Computational studies shown that rate-determining step, non-covalent interactions between amide moiety ligand benzene cyclohexane moieties substrate play key role stereocontrol during

Language: Английский

Citations

1
Enantioselective Synthesis of Axially and Centrally Chiral Styrenes via Nickel-Catalyzed Desymmetric Hydrocyanation of Biaryl Dienes DOI
Can Li,

Song‐Zhou Cai,

Juntao Ye

et al.

Organic Letters, Journal Year: 2024, Volume and Issue: 26(18), P. 3867 - 3871

Published: May 1, 2024

Herein, a highly regio-, enantio-, and diastereoselective nickel-catalyzed desymmetric hydrocyanation of biaryl dienes for the simultaneous construction axial central chiralities is presented, which offers convenient approach to variety tirenes containing union an axially chiral centrally α-chiral nitrile under mild conditions using commercially available catalyst. The synthetic utility highlighted by development novel phosphine ligand biphenyl-based diene their potential applications in field asymmetric catalytic reactions.

Language: Английский

Citations

8
Metallaphotoredox-Catalyzed Three-Component Asymmetric Cross-Electrophile Coupling for Chiral Boronate Synthesis DOI
Xiaofang Li, Yuntong Hu,

Zhonghou Huang

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(20), P. 15790 - 15798

Published: Oct. 10, 2024

Here, we report a photoredox and nickel-catalyzed cross-electrophile coupling strategy for the asymmetric three-component 1,2-alkylarylation of vinyl boronates with (hetero)aryl bromides (2°, 3°)-alkyl redox-active esters in presence Hantzsch ester. With fluorinated pyridyl-substituted chiral biimidazoline ligand, this reaction enables straightforward access to wide variety synthetically valuable α-aryl from readily available starting materials. This features mild conditions, broad substrate generality, good functional group tolerance proceeds without using metal reductants or alkyl halides. Furthermore, alkenyl halides other electron-deficient alkenes such as acrylates phosphonates can be applied successfully. Preliminary mechanistic studies shed light on potential pathways roles organic amines.

Language: Английский

Citations

7
Ni-catalysed remote C(sp3)–H functionalization using chain-walking strategies DOI
Ciro Romano, Rubén Martı́n

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: unknown

Published: Oct. 1, 2024

Language: Английский

Citations

6
Recent Advances in Ni‐Catalyzed 1,1‐Difunctionalization of Unactivated Olefins DOI Open Access
Álvaro Velasco‐Rubio, Rubén Martı́n

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 366(4), P. 593 - 602

Published: Dec. 7, 2023

Abstract Unactivated olefins rank amongst the most important feedstocks in organic synthesis. Their availability makes them particularly useful synthons for subsequent functionalization, a catalytic manner. Driven by popularity ascribed nickel catalysis as new tool to rapidly forge molecular architectures via one‐or two‐electron manifolds, recent years have witnessed significant advances Ni‐catalyzed olefin difunctionalization. While 1,2‐difunctionalization or remote functionalization “chain‐walk” become mature disciplines repurposing potential of building blocks, it was only recently that extensions this chemistry 1,1‐difunctionalization been possible. This review summarizes 1,1‐difunctionalization, holding considerable promise powerful strategy our ever‐growing synthetic repertoire.

Language: Английский

Citations

13
Regio- and Diastereoselective Highly Strained Alkylidenecyclobutane Isomerization/Hydroacylation: Synthesis of Multisubstituted Cyclobutanes with Consecutive Stereocenters DOI

Kai-Qiang Tian,

Shi‐Jiao Zhang,

Jun Zhao

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(3), P. 1505 - 1513

Published: Jan. 16, 2024

The regio- and diastereoselective alkene isomerization hydrofunctionalization sequence enabled by transition-metal complexes allows rapid activation assembly of the C(sp3)–H bond that is either adjacent or distal to initial double bond, which has been a longstanding challenge in this field. Herein, we develop unusual rhodium-catalyzed alkylidenecyclobutanes with subsequent hydroacylation reaction provide multisubstituted cyclobutanes continuous stereocenters. Note tandem process features good diastereoselectivity profile. Isotopic labeling experiments support "exo endo" migration coordinated cyclobutene responsible for deuterium incorporation observed cyclobutane product.

Language: Английский

Citations

5
Enantioselective Synthesis of β-Aminoboronic Acids via Borylalkylation of Enamides DOI
Liguo Lu, Shuhan Chen, Weiyu Kong

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(24), P. 16639 - 16647

Published: June 10, 2024

Aminoboronic acids represent a class of significant compounds that have attracted attention in the fields drug discovery and organic synthesis. Despite notable progress their synthesis, efficient construction chiral β-aminoboronic with alkyl side chains remains challenging endeavor. Here, we introduce an unprecedented nickel-catalyzed asymmetric borylalkylation enamides, employing simple diamine ligand, readily available B2pin2, halides as coupling partners. This reaction serves platform for assembling diverse range acid derivatives flexible chains, displaying exceptional regio-, stereo-, enantioselectivities. Moreover, this transformation exhibits broad substrate scope remarkable tolerance toward various functional groups. Theoretical calculations demonstrate benzyl group on ligand is key to high enantiocontrol transformation. Additionally, exemplify practical application strategy through concise synthesis complex bioactive molecules.

Language: Английский

Citations

5
Stereoselective Construction of Multifunctional C-Glycosides Enabled by Nickel-Catalyzed Tandem Borylation/Glycosylation DOI
Xiaomei Wu, Shijia Li, Liqin Chen

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(32), P. 22413 - 22423

Published: Aug. 3, 2024

Stereochemically pure saccharides have indispensable roles in fields ranging from medicinal chemistry to materials science and organic synthesis. However, the development of a simple, stereoselective, efficient glycosylation protocol access α- β-C-glycosides (particularly 2-deoxy entities) remains persistent challenge. Existing studies primarily focused on C1 modification carbohydrates transformation glycosyl radical precursors. Here, we innovate by harnessing situ generated glycosyl-Ni species achieve one-pot borylation cascade manner, which is enabled an earth-abundant nickel-catalyzed carboboration readily accessible glycals without any ligand. This work reveals potential for modular multifunctional platform facilitate simultaneous introduction C-C C-B bonds at stereogenic center saccharides, largely unexploited research area. Preliminary experimental computational indicate that endocyclic O C3 group play important stereoseclectively forging glycosidic bonds. As result, diverse range C-R (R = alkyl, aryl, alkenyl) 2-deoxygenated glycosides bearing modifiable boron groups could be rapidly made with excellent stereocontrol exhibit remarkable functional tolerance. The synthetic underscored late-stage natural products commercial drugs as well facile preparation various rare sugars, bioactive conjugates, key intermediates prorocentin, phomonol, aspergillide A.

Language: Английский

Citations

5