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

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

---

Well-Defined Phosphine-Free Manganese(II)-Complex-Catalyzed Synthesis of Quinolines, Pyrroles, and Pyridines

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(13), P. 8351 - 8367

Published: June 21, 2022

Herein, we report a simple, phosphine-free, and inexpensive catalytic system based on manganese(II) complex for synthesizing different important N-heterocycles such as quinolines, pyrroles, pyridines from amino alcohols ketones. Several control experiments, kinetic studies, DFT calculations were carried out to support the plausible reaction mechanism. We also detected two potential intermediates in cycle using ESI-MS analysis. Based these metal-ligand cooperative mechanism was proposed.

Language: Английский

---

Designing Cobalt(II) Complexes for Tandem Dehydrogenative Synthesis of Quinoline and Quinazoline Derivatives

Organic Letters, Journal Year: 2024, Volume and Issue: 26(2), P. 514 - 518

Published: Jan. 9, 2024

In this work, we have constructed three new Co(II) complexes in which steric features govern their structural geometry. The metal ligand-cooperation behavior of the alkoxy arm is utilized to explore catalytic activities these with respect dehydrogenation. A wide range C-3-substituted quinoline and quinazoline derivatives were synthesized high yields. developed protocol's usefulness enhanced by chemoselective transformation different fatty alcohols synthesize heterocycles having distal unsaturation. Various kinetic, mechanistic, control studies conducted comprehend reaction route.

Language: Английский

---

Well-Defined NNS-Mn Complex Catalyzed Selective Synthesis of C-3 Alkylated Indoles and Bisindolylmethanes Using Alcohols

The Journal of Organic Chemistry, Journal Year: 2022, Volume and Issue: 87(6), P. 3989 - 4000

Published: March 8, 2022

Herein, we demonstrated Mn-catalyzed selective C-3 functionalization of indoles with alcohols. The developed catalyst can also furnish bis(indolyl)methanes from the same set substrates under slightly modified reaction conditions. Mechanistic studies reveal that is going via a borrowing hydrogen pathway. To highlight practical utility, diverse range including nine structurally important drug molecules are synthesized. Furthermore, introduced one-pot cascade strategy for synthesizing functionalized directly 2-aminophenyl ethanol and alcohol.

Language: Английский

---

A general and practical bifunctional cobalt catalytic system for N-heterocycle assembly via acceptorless dehydrogenation

Organic Chemistry Frontiers, Journal Year: 2022, Volume and Issue: 9(17), P. 4554 - 4560

Published: Jan. 1, 2022

A novel and highly-efficient N-heterocycle assembly methodology catalyzed by a cobalt- N , -bidentate complex via acceptorless dehydrogenation coupling of alcohols amines has been established.

Language: Английский

---

Zn(II)-Catalyzed Multicomponent Sustainable Synthesis of Pyridines in Air

The Journal of Organic Chemistry, Journal Year: 2023, Volume and Issue: 88(6), P. 3650 - 3665

Published: Feb. 28, 2023

Herein, we report a Zn(II)-catalyzed solvent-free sustainable synthesis of tri- and tetra-substituted pyridines using alcohols as the primary feedstock NH4OAc nitrogen source. Using well-defined air-stable Zn(II)-catalyst, 1a, featuring redox-active tridentate azo-aromatic pincer, 2-((4-chlorophenyl)diazenyl)-1,10-phenanthroline (La), wide variety unsymmetrical 2,4,6-substituted were prepared by three-component coupling secondary with NH4OAc. Catalyst 1a is equally compatible four-component coupling. Unsymmetrical also via alcohol two different A series up to 67% yield 1-phenylpropan-1-one or 1,2-diphenylethan-1-one The 1a-catalyzed reactions proceeded efficiently upon replacing corresponding ketones, producing desired in higher yields shorter reaction time. few control experiments performed unveil mechanistic aspects, which indicates that active participation aryl-azo ligand during catalysis enables Zn(II)-complex act an efficient catalyst for present multicomponent reactions. Aerial oxygen acts oxidant dehydrogenation alcohols, H2O H2O2 byproducts.

Language: Английский

---

Zn(II)‐Stabilized Azo‐Anion Radical Catalyzed Sustainable C−C Bond Formation: Regioselective Alkylation of Fluorene, Oxindole, and Indoles

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(10)

Published: Feb. 7, 2024

Abstract Herein we report a sustainable approach for the alkylation of ketones, 9 H ‐fluorene, oxindole, and indole using alcohols as alkylating agent catalyzed by well‐defined air‐stable zinc catalyst ( 1 ) tridentate redox non‐innocent arylazo ligand, 2‐((4‐chlorophenyl)diazenyl)‐1,10‐phenanthroline L ). 2–3 mol % efficiently produces substituted α‐alkylated 9‐alkylated fluorenes, C3 ‐alkylated oxindoles, indoles in moderate to good isolated yields. In aerial condition, formation bis(indolyl)methane (BIMs) derivatives were observed when subjected primary alcohols. A few drug molecules containing BIMs prepared The exhibited chemoselectivity during functionalization fluorene with oleyl alcohol β‐citronellol. control experiments, including deuterium labeling performed unveil reaction mechanism indicate that one‐electron reduced azo‐anion radical species [ ]‐formed situ, acts active catalyst. All events occur at redox‐active aryl‐azo which reservoir hydrogen electrons throughout catalytic cycle, keeping Zn(II)‐center template.

Language: Английский

---

Well‐Defined Ni−SNS Complex Catalysed Borrowing Hydrogenative α‐Alkylation of Ketones and Dehydrogenative Synthesis of Quinolines

Advanced Synthesis & Catalysis, Journal Year: 2022, Volume and Issue: 364(14), P. 2429 - 2437

Published: May 23, 2022

Abstract The “borrowing hydrogen” (BH) method for C‐alkylation reactions using alcohol as alkylating agents is an important synthetic transformation. In this respect, designing cheap and bench stable earth abundant metal catalyst borrowing hydrogen transformation a key challenge to be witnessed. Herein we have presented synthesis of non‐phosphine, easily accessible SNS−Ni complexes. Ni‐catalyst was successfully applied the ketone enolates α‐alkylated ketones. Primary with different functional groups various heteroaromatic alcohols are well tolerated. present system efficiently gram scale also green chemistry metrics reaction were calculated. protocol extended biologically quinoline moieties. Finally, control experiments deuterium labelled suggest that proceeds via pathway. magnified image

Language: Английский

---

Strategies and Methods for the Synthesis of 2‐Pyrazolines: Recent Developments (2012–2022)

Advanced Synthesis & Catalysis, Journal Year: 2023, Volume and Issue: 365(12), P. 1934 - 1969

Published: May 22, 2023

Abstract 2‐Pyrazolines are important five‐membered heterocycles, containing two adjacent nitrogen atoms. They can incorporate various functional groups and possess unique biological properties. Moreover, they have been used as useful building blocks. In recent years, the field of 2‐pyrazoline synthesis has experienced enormous progress. Novel strategies developed, many studies reporting improvements or adaptations existing protocols published, giving access to new functionalizations, unexplored structures, and/or enantioselective synthesis. This review summarizes progress made in synthetic methodologies during period from 2012 2022. The functionalization challenges capabilities, scopes limitations reactions, substitution patterns, mechanisms where appropriate, will be discussed.

Language: Английский

---

Manganese catalyzed switchable C-alkylation/alkenylation of fluorenes and indene with alcohols

Chemical Communications, Journal Year: 2021, Volume and Issue: 57(80), P. 10363 - 10366

Published: Jan. 1, 2021

The usage of earth-abundant, nontoxic transition metals in place rare noble is a central goal catalysis.

Language: Английский

---