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

Chemical Reviews, Год журнала: 2024, Номер 124(9), С. 6078 - 6144

Опубликована: Апрель 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

Язык: Английский

---

Harnessing alcohols as sustainable reagents for late-stage functionalisation: synthesis of drugs and bio-inspired compounds

Chemical Society Reviews, Год журнала: 2024, Номер 53(9), С. 4607 - 4647

Опубликована: Янв. 1, 2024

This review collectively discussed the utilisation of alcohols in various organic transformations and their application toward intermediates drugs, drug derivatives natural product-like molecules.

Язык: Английский

---

Divergent Synthesis of Alcohols and Ketones via Cross‐Coupling of Secondary Alcohols under Manganese Catalysis

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(26)

Опубликована: Апрель 21, 2023

A homogeneous manganese-catalyzed cross-coupling of two secondary alcohols for the divergent synthesis γ-disubstituted and β-disubstituted ketones is reported. Employing well-defined Mn-MACHOPh as catalyst, this novel protocol has a broad substrate scope with good functional group tolerance affords diverse library valuable disubstituted in moderate to yields. The strong influence reaction temperature on selective formation alcohol products was theorized preliminary DFT studies. Studies have shown that Gibbs free energy thermodynamically more favourable than corresponding at lower temperature.

Язык: Английский

---

Ruthenium pincer complex catalyzed efficient synthesis of quinoline, 2-styrylquinoline and quinazoline derivatives via acceptorless dehydrogenative coupling reactions

Catalysis Science & Technology, Год журнала: 2022, Номер 12(18), С. 5695 - 5702

Опубликована: Янв. 1, 2022

The synthesis of N-heterocycles has been considered an emerging area chemical research due to their extensive utilization in pharmaceuticals, materials science, and natural product synthesis.

Язык: Английский

---

Guerbet-type β-alkylation of secondary alcohols catalyzed by chromium chloride and its corresponding NNN pincer complex

Catalysis Science & Technology, Год журнала: 2022, Номер 12(15), С. 4753 - 4762

Опубликована: Янв. 1, 2022

β-Alkylation of alcohols has been efficiently accomplished using readily available 3d metal Cr under microwave conditions in air. Well-defined molecular is involved with a KIE 7.33 and insertion α-alkylated ketone into Cr–H bond as the RDS.

Язык: Английский

---

Recent Advances for Alkylation of Ketones and Secondary Alcohols Using Alcohols in Homogeneous Catalysis

Advanced Synthesis & Catalysis, Год журнала: 2022, Номер 364(18), С. 3100 - 3121

Опубликована: Июль 4, 2022

Abstract The alkylation of ketones or secondary alcohols using as alkylating agents via hydrogen borrowing strategy presents a powerful method for the synthesis ɑ‐alkylated ketones. In this review, we summarize progress catalyzed by Ir, Pd, Rh, Ru, Mn, Fe, Co, Ni, and Cu catalysts α‐alkylation with cross‐coupling from 2017 to 2021. A wide range (aromatic aliphatic ketones) (benzylic primary alcohols, aromatic alkenyl diols) are well tolerated. Furthermore, also discuss current challenges propose perspectives on coming development in filed. objective present review is give an overview recent advances β‐alkylation alcohols. Finally, hope that will inspirations magnified image

Язык: Английский

---

Manganese‐Catalyzed Chemoselective Coupling of Secondary Alcohols, Primary Alcohols and Methanol

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(17)

Опубликована: Фев. 27, 2023

Herein, we report a manganese-catalyzed three-component coupling of secondary alcohols, primary alcohols and methanol for the synthesis β,β-methylated/alkylated alcohols. Using our method, series 1-arylethanol, benzyl alcohol derivatives, undergo sequential efficiently to construct assembled with high chemoselectivity in moderate good yields. Mechanistic studies suggest that reaction proceeds via methylation benzylated intermediate generate final product.

Язык: Английский

---

NNN manganese complex-catalyzed α-alkylation of methyl ketones using alcohols: an experimental and computational study

Dalton Transactions, Год журнала: 2024, Номер 53(7), С. 3236 - 3243

Опубликована: Янв. 1, 2024

A quinoline-based pincer Mn catalyst for α-alkylation of methyl ketones using primary alcohols as alkyl surrogates is presented. The C–C bond formation reaction proceeds via a hydrogen auto-transfer protocol, generating water the only by-product.

Язык: Английский

---

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

Advanced Synthesis & Catalysis, Год журнала: 2022, Номер 364(14), С. 2429 - 2437

Опубликована: Май 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

Язык: Английский

---

Pincer-Cobalt-Catalyzed Guerbet-Type β-Alkylation of Alcohols in Air under Microwave Conditions

Organometallics, Год журнала: 2022, Номер 41(22), С. 3387 - 3398

Опубликована: Авг. 5, 2022

Pincer complexes of the type (R2NNN)CoCl2 (R = iPr, tBu, Cy, Ph, p-F-C6H4) derived from environmentally benign, earth-abundant, and inexpensive base metal cobalt have been synthesized that exist in equilibrium with [(R2NNN)2Co]CoCl4. Among these complexes, (iPr2NNN)CoCl2 has found to be highly efficient for catalytic β-alkylation alcohols air at 140 °C. While pincer-Co (0.0025 mol %)-catalyzed presence NaOtBu (2.5 %) took 24 h (85%, 34000 TON 1417 TO/h) under conventional heating (140 °C), corresponding reaction microwave conditions °C 75 W) was complete only 2 comparable yields (83%, 33200 TON), albeit a better TOF (16600 TO/h). In contrast, CoCl2 otherwise identical leads lower both (66%, 26400 1100 (61%, 24400 12200 The system successfully implemented (39 examples) accomplish secondary several primary alcohols. Well-defined molecular Co(II) species are involved during catalysis, as inferred HRMS hot-filtration experiments. EPR studies magnetic moment measurements using Evans method demonstrate Co remains its +2 state an octahedral geometry throughout reaction. Pivotal evidence involvement β-hydride elimination leading acetophenone RDS catalyzed is obtained competitive deuterium labeling experiments, which indicative KIE 6.14. current report on base-metal catalysis high unprecedented turnovers (33200 16600 very short time (2 h) offers exciting atom-economical greener possibilities class synthetically valuable Guerbet-type reactions.

Язык: Английский

---