Direct site-selective C(sp<sup>3</sup>)–H functionalization of unprotected non-activated alcohols DOI
Vaneet Aggarwal, Ankit Kachore, Ekta Bala

et al.

Russian Chemical Reviews, Journal Year: 2024, Volume and Issue: 93(6), P. RCR5123 - RCR5123

Published: June 1, 2024

Free alcohols are ubiquitous in nature, drugs, bulk chemicals, and various complex molecules. The abundantly available free aliphatic alcohols, being inexpensive, sustainable starting materials organic synthesis to construct value-added scaffolds. Direct C(sp<sup>3</sup>)–H functionalization of inert bonds alcoholic chain is challenging due their inactive nature towards chemical reactions also multiple similar C–H for reaction at a time. Barton process, which classical method generating alkoxyl radicals, has been widely used the remote using strategy 1,5-hydrogen atom transfer (1,5-HAT). However, requirement pre-activation not only adds extra tedious steps but also, these precursors prepare handle. Generating desired radicals from difficult task affects economy reactions. Numerous methods covering unprotected non-activated diverse (α-, β-, γ-, δ-) positions access functionalized elaborated here. A precise focused compilation will help understand what established how new methodologies can be developed future needs. <br> bibliography includes 158 references.

Language: Английский

Alcohols as Substrates in Transition-Metal-Catalyzed Arylation, Alkylation, and Related Reactions DOI

Adam Cook,

Stephen G. Newman

Chemical Reviews, Journal Year: 2024, Volume and Issue: 124(9), P. 6078 - 6144

Published: April 17, 2024

Alcohols are abundant and attractive feedstock molecules for organic synthesis. Many methods their functionalization require them to first be converted into a more activated derivative, while recent years have seen vast increase in the number of complexity-building transformations that directly harness unprotected alcohols. This Review discusses how transition metal catalysis can used toward this goal. These broadly classified three categories. Deoxygenative functionalizations, representing derivatization C–O bond, enable alcohol act as leaving group formation new C–C bonds. Etherifications, characterized by O–H represent classical reactivity has been modernized include mild reaction conditions, diverse partners, high selectivities. Lastly, chain reactions described, wherein acts mediator formal C–H alkyl backbone. Each these classes transformation will discussed context intermolecular arylation, alkylation, related reactions, illustrating alcohols harnessed

Language: Английский

Citations

39
A modular approach to catalytic stereoselective synthesis of chiral 1,2-diols and 1,3-diols DOI Creative Commons
Sheng Xu, Yuanyuan Ping,

Yinyan Su

et al.

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

Published: Jan. 3, 2025

Optically pure 1,2-diols and 1,3-diols are the most privileged structural motifs, widely present in natural products, pharmaceuticals chiral auxiliaries or ligands. However, their synthesis relies on use of toxic expensive metal catalysts suffer from low regioselectivity. Catalytic asymmetric optically 1,n-diols bulk chemicals a highly stereoselective atom-economical manner remains formidable challenge. Here, we disclose versatile modular method for enantioenriched high-production-volume ethane-1,2-diol (MEG) 1,3-propanediol (PDO), respectively. The key to success is temporarily mask diol group as an acetonide, which imparts selectivity step C(sp3)-H functionalization. Additionally, containing two stereogenic centers also prepared through diastereoselective late-stage functionalization biological active compounds expedient ligands pharmaceutically relevant molecules further highlight synthetic potential this protocol. authors report ethylene glycol 1,3-propanediol,

Language: Английский

Citations

3
Asymmetric Synthesis of Trisubstituted Vicinal Diols through Copper(I)‐Catalyzed Diastereoselective and Enantioselective Allylation of Ketones with Siloxypropadienes DOI
Nan Jiang,

Pei‐Zhi Liu,

Zhi‐Zhou Pan

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(21)

Published: Feb. 27, 2024

Chiral trisubstituted vicinal diols are a type of important organic compounds, serving as both common structure units in bioactive natural products and chiral auxiliaries asymmetric synthesis. Herein, by using siloxypropadienes the precursors allyl copper(I) species, copper(I)-catalyzed diastereoselective enantioselective reductive allylation ketones was achieved, providing syn-diols anti-diols good to excellent enantioselectivity. DFT calculations show that cis-γ-siloxy-allyl copper species generated favorably with either 1-TBSO-propadiene or 1-TIPSO-propadiene. Moreover, steric difference TBS group TIPS distinguishes face selectivity acetophenone, leading syn-selectivity for anti-selectivity Easy transformations were performed, demonstrating synthetic utility present method. one diol prepared above used suitable organocatalyst catalytic self-coupling aldimines situ B

Language: Английский

Citations

8
Carbonyl Allylation and Crotylation: Historical Perspective, Relevance to Polyketide Synthesis, and Evolution of Enantioselective Ruthenium-Catalyzed Hydrogen Auto-Transfer Processes DOI
Eliezer Ortiz,

Connor Saludares,

Jessica Wu

et al.

Synthesis, Journal Year: 2023, Volume and Issue: 55(10), P. 1487 - 1496

Published: Feb. 20, 2023

Abstract The evolution of methods for carbonyl allylation and crotylation alcohol proelectrophiles culminating in the design iodide-bound ruthenium-JOSIPHOS catalysts is prefaced by a brief historical perspective on asymmetric its relevance to polyketide construction. Using gaseous allene or butadiene as precursors allyl- crotylruthenium nucleophiles, respectively, new capabilities have been unlocked, including stereo- site-selective 1,3-diols related polyols. 1 Introduction Historical Perspective 2 Ruthenium-Catalyzed Conversion Lower Alcohols into Higher 3 Conclusion Future Outlook

Language: Английский

Citations

14
A Hydrogen Evolution Catalyst [Co2O2] Metallacycle Enables Regioselective Allene C(sp2)‐H Functionalization DOI

Yating Liang,

Jiayi Feng,

Huilong Li

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(15)

Published: Feb. 8, 2024

Abstract Selective functionalization of allenic C(sp 2 )‐H is an ideal approach to upgrading simple allenes synthetically useful allenes, albeit suffering from challenges associated with inert reactivity and inferior selectivity. Inspired by energy chemistry, a catalytic hydrogen evolution reaction (HER) strategy was leveraged selectively activate weakly acidic allene bonds in reductive mode. An array [Co O ] metallacycle complexes were readily devised starting amino acids, they demonstrated as robust HER catalysts, which would break release hydrogen. With the newly developed catalyst, regioselective electrochemical alcoholic α 3 unprecedentedly achieved. This features excellent regioselectivity, unconventional chemoselectivity, good functional‐group tolerance (62 examples), mild conditions. Mechanism experiments revealed reactive hydroxy‐coordinated cobalt(II) species reaction. Density functional theory (DFT) calculations also conducted rationalize regioselectivity observed

Language: Английский

Citations

6
Leveraging the Stereochemical Complexity of Octahedral Diastereomeric-at-Metal Catalysts to Unlock Regio-, Diastereo-, and Enantioselectivity in Alcohol-Mediated C–C Couplings via Hydrogen Transfer DOI
Jonathan Z. Shezaf, Catherine G. Santana, Eliezer Ortiz

et al.

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: 146(12), P. 7905 - 7914

Published: March 13, 2024

Experimental and computational studies illuminating the factors that guide metal-centered stereogenicity and, therefrom, selectivity in transfer hydrogenative carbonyl additions of alcohol proelectrophiles catalyzed by chiral-at-metal-and-ligand octahedral d6 metal ions, iridium(III) ruthenium(II), are described. To augment or invert regio-, diastereo-, enantioselectivity, predominantly one from among as many 15 diastereomeric-at-metal complexes is required. For catalysts, cyclometalation assists defining stereocenter, for ruthenium(II) iodide counterions play a key role. Whereas classical strategies to promote catalysis aim high-symmetry transition states, well-defined low-symmetry states can unlock selectivities otherwise difficult achieve inaccessible.

Language: Английский

Citations

6
Integrating MOF‐Based Catalysis with Nanocavity‐Confined Pd Catalysis over Multifunctional Pd‐MOF‐Fe for Acceptorless Dehydrogenation of Alcohols under Visible Light DOI

Shiqin Lai,

Zhibing Kang,

L.J. Zhang

et al.

ChemistrySelect, Journal Year: 2024, Volume and Issue: 9(1)

Published: Jan. 2, 2024

Abstract Solar‐driven hydrogen (H 2 ) evolution combined with synchronously selective oxidation for fine chemicals production is of great significance in energy and synthetic chemistry. Herein, ultrafine Pd nanoparticles‐encapsulated MIL‐100(Fe) (Pd‐MOF‐Fe) nanocomposites are synthesized through double‐solvent impregnation integrated photo‐reduction method. Integrating MOF‐based catalysis Pd‐based catalysis, the Pd‐MOF‐Fe can serve as multifunctional catalyst photoinduced alcohol dehydrogenation reaction. Optimal generation rates H (3.61 mmol g −1 h benzaldehyde (3.40 gained over Pd‐MOF‐Fe, ca. 4.1 times that Pd/MOF‐Fe, which crystals size ranging from 3 to 6 nm immobilized on intersurface MOFs. Besides, controlled experiments reveal pivotal role opened FeO nodes Lewis acid sites toward activation. This work provides a controllable approach metal nanoparticle immobilization. Furthermore, considering diversified MOF structures, this study also highlights infinite possibility nanoparticle/MOFs platform solar conversion production.

Language: Английский

Citations

3
Formate-Mediated C–C Coupling of Aryl/Vinyl Halides and Triflates: Carbonyl Arylation and Reductive Cross-Coupling DOI
Yu-Hsiang Chang, Yoon Cho, Weijia Shen

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 8274 - 8283

Published: May 2, 2025

Language: Английский

Citations

0
Engineering Limonene Epoxide Hydrolases for the Enantiocomplementary Synthesis of Chiral 1,3-Diols and Oxetanes DOI

Zhouzhou Zhao,

Jun‐Kuan Li,

Congcong Li

et al.

ACS Catalysis, Journal Year: 2025, Volume and Issue: unknown, P. 9201 - 9209

Published: May 15, 2025

Language: Английский

Citations

0
Catalytic Enantioselective C–C Coupling of Alcohols for Polyketide Total Synthesis beyond Chiral Auxiliaries and Premetalated Reagents DOI
Jessica Wu,

Katherine L. Verboom,

Michael J. Krische

et al.

Chemical Reviews, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 6, 2024

Catalytic enantioselective hydrogen autotransfer reactions for the direct conversion of lower alcohols to higher are catalogued and their application total synthesis polyketide natural products is described. These methods exploit a redox process in which alcohol oxidation balanced by reductive generation organometallic nucleophiles from unsaturated hydrocarbon pronucleophiles. Unlike classical carbonyl additions, premetalated reagents, chiral auxiliaries discrete alcohol-to-aldehyde not required. Additionally, chemoselective dehydrogenation primary presence secondary enables C-C coupling absence protecting groups.

Language: Английский

Citations

1