Alcohols as Alkyl Synthons Enabled by Photoredox-Catalyzed Deoxygenative Activation DOI

Tanumoy Mandal,

Samrat Mallick,

Malekul Islam

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: 14(17), P. 13451 - 13496

Published: Aug. 26, 2024

Alcohols are abundant with versatile structural variety and have ample use as pivotal functional groups in numerous organic processes. Because of their frequent occurrence enumerable natural products, bioactive molecules, medicinal components, alcohol functionalities provide a promising scope research to advance the operational diversity for improving clinical success. Recent years witnessed design modern C–C C–heteroatom bond-forming approaches easily accessible commercially available unactivated aliphatic alcohols native adaptive sp3 handles, hence offering groundbreaking transformative pathways functionalization complex molecular architectures. The judicial application appropriate activating generate alkyl radical from through C–O bond fragmentation employ it potential alkylating agent unfolds unique synthetic strategies, thereby replacing obvious requirement halides. This review elaborately discusses recent trends regarding using C(sp3)-centered various chemical transformations by exploiting different activation modes disrupter under photoredox catalysis. presentation is organized nature scaffolds, kind formation, progress achieved this domain since original discovery providing illustrative examples mechanistic details, focus on difficulties future prospects.

Language: Английский

Design and Application of Chiral Bifunctional 4-Pyrrolidinopyridines: Powerful Catalysts for Asymmetric Cycloaddition of Allylic N-Ylide DOI

Qing-Qing Luo,

Zhou Tian, Jie Tang

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(12), P. 7221 - 7232

Published: June 2, 2022

We designed bifunctional 4-pyrrolidinopyridines as powerful Lewis base catalysts. The catalyst structure features a 4-hydroxy-2-(hydroxydiphenylmethyl)pyrrolidine-1-formyl group at the pyridine's C3 site and chiral side arm C2 position of p-pyrrolidine ring. An operationally simple three-step synthetic route allows for efficient economical preparation. In comparison with other bases, exhibits excellent efficiency stereoselectivity in asymmetric (3 + 2) cycloaddition allylic N-ylide generated situ from pyrazolone-derived Morita–Baylis–Hillman carbonate, providing platform construction spiropyrazolone derivatives. reaction mechanism was thoroughly studied. Control experiments DFT calculations illustrated origin chemoselectivity stereocontrol model. H-bonding is crucial control enantioselectivity diastereoselectivity. also successfully applied reactions, such an acylative dynamic kinetic resolution to synthesize phthalidyl ester, including prodrug Talmetacin.

Language: Английский

Citations

44
Copper-Catalyzed Yne-Allylic Substitutions Using Stabilized Nucleophiles DOI

Shengtong Niu,

Yingkun Luo,

Chao Xu

et al.

ACS Catalysis, Journal Year: 2022, Volume and Issue: 12(12), P. 6840 - 6850

Published: May 25, 2022

Using stabilized "soft" nucleophiles in copper-catalyzed allylic substitutions is highly desirable but remains an unsolved challenge for the last 40 years. In this work, a general protocol of using such as indoles, pyrroles, amines, and 1,3-dicarbonyls has been developed, delivering large variety functionalized 1,3- 1,4-enynes with high levels regio- stereoselectivities (67 examples). A range further transformations products can be easily achieved to release various molecules. mechanistic rationale copper acetylide-bonded cation key intermediate that features outer-sphere nucleophilic attack proposed. Additionally, series diversified reactivities have demonstrated, which will inspire studies.

Language: Английский

Citations

40
Synthesis of Chiral Endocyclic Allenes by Palladium‐Catalyzed Asymmetric Annulation Followed by Cope Rearrangement DOI

Bin Shi,

Jiabin Liu,

Ze‐Tian Wang

et al.

Angewandte Chemie International Edition, Journal Year: 2022, Volume and Issue: 61(24)

Published: March 25, 2022

Catalytic asymmetric synthesis of chiral endocyclic allenes remains a challenge in allene chemistry owing to unfavored tension and complex chirality. Here, we present new relay strategy merging Pd-catalyzed [3+2] annulation with enyne-Cope rearrangement, providing facile route 9-membered high efficiency enantioselectivity. Moreover, theoretical calculations experimental studies were performed illustrate the critical, but unusual Cope rearrangement that allows for complete central-to-axial chirality transfer.

Language: Английский

Citations

39
Copper-catalysed convergent regio- and enantioselective alkynylallylic substitution DOI

Jiang-Shan Ma,

Han-Yu Lu,

Ye‐Wei Chen

et al.

Nature Synthesis, Journal Year: 2022, Volume and Issue: 2(1), P. 37 - 48

Published: Oct. 24, 2022

Language: Английский

Citations

39
The green chemistry paradigm in modern organic synthesis DOI
Sergei G. Zlotin, Ksenia S. Egorova, Valentine P. Ananikov

et al.

Russian Chemical Reviews, Journal Year: 2023, Volume and Issue: 92(12), P. RCR5104 - RCR5104

Published: Dec. 1, 2023

After the appearance of green chemistry concept, which was introduced in vocabulary early 1990s, its main statements have been continuously developed and modified. Currently, there are 10–12 cornerstones that should form basis for an ideal chemical process. This review analyzes accumulated experience achievements towards design products processes reduce or eliminate use generation hazardous substances. The presents views leading Russian scientists specializing various fields this subject, including homogeneous heterogeneous catalysis, fine basic organic synthesis, electrochemistry, polymer chemistry, based on bio-renewable feedstocks energetic compounds materials. A new approach to quantitative evaluation environmental friendliness by authors is described. <br> bibliography includes 1761.

Language: Английский

Citations

39
Enantio‐ and Diastereoselective Synthesis of Chiral Tetrasubstituted α‐Amino Allenoates Bearing a Vicinal All‐Carbon Quaternary Stereocenter with Dual‐Copper‐Catalysis DOI

Cheng Sheng,

Zheng Ling, Junzhe Xiao

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(31)

Published: June 1, 2023

The skeletons of chiral tetrasubstituted allenes bearing a vicinal all-carbon quaternary stereocenter are importance but still challenging to synthesize. Herein, we report enantio- and diastereoselective γ-additions 1-alkynyl ketimines with dual-copper-catalysis under mild conditions, affording α-amino allenoates in high yields (up 99 % yield) excellent enantioselectivities ee) diastereoselectivities >20 : 1 dr). Importantly, the stereodivergent synthesis products was realized by asymmetric γ-addition reaction Grignard reagent promoted epimerization. Moreover, dual-copper-catalyzed reactions were smoothly applied gram-scale adopted introduce allenyl moieties into bioactive molecules. Mechanistic experiments density functional theory (DFT) calculations demonstrated that catalyzed double copper catalysts.

Language: Английский

Citations

27
Enantioselective C3‐Allylation of Pyridines via Tandem Borane and Palladium Catalysis DOI

Jun‐Jie Tian,

Rui‐Rui Li,

Gui‐Xiu Tian

et al.

Angewandte Chemie International Edition, Journal Year: 2023, Volume and Issue: 62(34)

Published: July 3, 2023

Abstract Herein, we report a one‐pot method for enantioselective C−H allylation of pyridines at C3 via tandem borane and palladium catalysis. This involves borane‐catalyzed pyridine hydroboration to generate dihydropyridines, then palladium‐catalyzed the dihydropyridines with allylic esters, finally air oxidation allylated afford products. enables introduction an group excellent regio‐ enantioselectivities.

Language: Английский

Citations

26
Regio- and Enantioselective Allylic Cyanomethylation by Synergistic Rhodium and Silane Catalysis DOI

Minghe Sun,

Linsheng Wei,

Changkun Li

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(7), P. 3897 - 3902

Published: Feb. 8, 2023

Rh/silane-cocatalyzed regio- and enantioselctive allylic cyanomethylation with inert acetonitrile directly has been developed. Addition of a catalytic amount neutral silane reagent as an anion carrier is essential for the success this reaction. The synthesis mono- bis-allylation products can be switched by adjusting size substituents on silane, ligands, temperature. Chiral homoallylic nitriles could synthesized in above 20:1 branch/linear ratio, up to 98% yield >99% ee.

Language: Английский

Citations

24
Enantioselective Construction of Quaternary Stereocenters via Cooperative Photoredox/Fe/Chiral Primary Amine Triple Catalysis DOI
Lianjie Li,

J.Z.H. Zhang,

W. Li

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(13), P. 9404 - 9412

Published: March 20, 2024

The catalytic and enantioselective construction of quaternary (all-carbon substituents) stereocenters poses a formidable challenge in organic synthesis due to the hindrance caused by steric factors. One conceptually viable potentially versatile approach is coupling C–C bond through an outer-sphere mechanism, accompanied realization enantiocontrol cooperative catalysis; however, examples such processes are yet be identified. Herein, we present method for creating different compounds with photoredox/Fe/chiral primary amine triple catalysis. This facilitates connection unactivated alkyl source tertiary moiety, which also rare. scalable process exhibits mild conditions, does not necessitate use base, possesses good functional-group tolerance. Preliminary investigations into underlying mechanisms have provided valuable insights reaction pathway.

Language: Английский

Citations

13
Challenging Task of Ni-Catalyzed Highly Regio-/Enantioselective Semihydrogenation of Racemic Tetrasubstituted Allenes via a Kinetic Resolution Process DOI
Gang Liu,

Xuanliang Yang,

Pei Gu

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(11), P. 7419 - 7430

Published: March 6, 2024

The first earth-abundant transition metal Ni-catalyzed highly regio- and enantioselective semihydrogenation of racemic tetrasubstituted allenes via a kinetic resolution process as challenging task was well established. This protocol furnishes expedient access to diversity structurally important enantioenriched chiral allylic molecules with high regio-, enantio-, Z/E-selectivity. Remarkably, this proceeded one carbon–carbon double bond allenes, which regioselective complementary the Rh-catalyzed asymmetric version. Deuterium labeling experiments density functional theory (DFT) calculations were carried out reveal reasonable reaction mechanism explain regio-/stereoselectivity.

Language: Английский

Citations

12