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

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Cobalt‐Catalyzed Regiodivergent and Enantioselective Intermolecular Coupling of 1,1‐Disubstituted Allenes and Aldehydes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(19)

Опубликована: Март 3, 2023

Catalytic enantioselective coupling of 1,1-disubstituted allenes and aldehydes through regiodivergent oxidative cyclization followed by stereoselective protonation or reductive elimination promoted chiral phosphine-Co complexes is presented. Such processes represent unprecedented unique reaction pathways for Co catalysis that enable catalytic generation metallacycles with divergent regioselectivity accurately controlled ligands, affording a wide range allylic alcohols homoallylic are otherwise difficult to access without the need pre-formation stoichiometric amounts alkenyl- allyl-metal reagents in up 92 % yield, >98 : 2 regioselectivity, dr >99.5 0.5 er.

Язык: Английский

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

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(21)

Опубликована: Фев. 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

Язык: Английский

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

Synthesis, Год журнала: 2023, Номер 55(10), С. 1487 - 1496

Опубликована: Фев. 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

Язык: Английский

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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

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(12), С. 7905 - 7914

Опубликована: Март 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.

Язык: Английский

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Hydrogen Source Tuned Regiodivergent Asymmetric Hydroalkylations of 2‐Substituted 1,3‐Dienes with Aldehydes by Cobalt‐Catalysis

Angewandte Chemie International Edition, Год журнала: 2024, Номер 63(23)

Опубликована: Апрель 3, 2024

Abstract Catalytic methods allowing for the reliable prediction and control of diverse regioselectivity along with enantioselectivity to access different regio‐ enantiomers by switching least reaction parameters are one most attractive ways in organic synthesis, which provide enantioenriched architectures from identical starting materials. Herein, a Co‐catalyzed regiodivergent enantioselective reductive hydroalkylation 1,3‐dienes aldehydes has been achieved, furnishing homoallylic alcohol good levels enantioselectivity. The features switch tuned selection proton source. use an acid as source provided asymmetric 1,2‐hydroalkylation products under conditions, yet 4,3‐hydroalkylation were obtained silane hydride This catalytic protocol allows alcohols two continuous saturated carbon centers regio‐, diastereo‐,

Язык: Английский

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Ruthenium‐Catalyzed C−C Coupling of Terminal Alkynes with Primary Alcohols or Aldehydes: α,β‐Acetylenic Ketones (Ynones) via Oxidative Alkynylation

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(23)

Опубликована: Март 31, 2023

Abstract The first metal‐catalyzed oxidative alkynylations of primary alcohols or aldehydes to form α,β‐acetylenic ketones (ynones) are described. Deuterium labelling studies corroborate a novel reaction mechanism in which alkyne hydroruthenation forms transient vinylruthenium complex that deprotonates the terminal active alkynylruthenium nucleophile.

Язык: Английский

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Borrowing Hydrogen/Chiral Enamine Relay Catalysis Enables Diastereo- and Enantioselective β-C–H Functionalization of Alcohols

Journal of the American Chemical Society, Год журнала: 2025, Номер 147(9), С. 7721 - 7728

Опубликована: Фев. 25, 2025

We report herein an unprecedented borrowing hydrogen/chiral enamine relay catalysis strategy that enables a highly efficient enantioselective formal β-alkylation of simple alcohols using electron-deficient alkenes and especially nitroalkenes. A variety 1,4-difunctional products such as nitro are readily accessible in one waste-free step from feedstock excellent levels stereoselectivity. It is important to note the formed much higher diastereoselectivity than alone under identical conditions, highlighting unique advantage cascade hydrogen achieving high efficiency, economy,

Язык: Английский

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Ruthenium-Catalyzed Transfer Hydrogenation of Alkynes: Access to Alkanes and (E)- or (Z)-Alkenes in Tandem with Pd/Cu Sonogashira Cross-Coupling

The Journal of Organic Chemistry, Год журнала: 2025, Номер unknown

Опубликована: Фев. 27, 2025

A complete reduction of alkynes using a combination [RuCl2(p-cymene)]2, DTBM-SEGPHOS, and paraformaldehyde/water system as the hydrogen source was developed, affording alkanes in 52–99% yields. In addition, preparation alkenes from terminal aryl iodides by tandem process Pd/Cu-catalyzed Sonogashira reaction followed Ru-catalyzed transfer hydrogenation is reported, 38–99% This multicatalysis proceeds via three consecutive reactions can be extended further, shown adding an iodine-catalyzed cis–trans alkene isomerization step.

Язык: Английский

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Formal Synthesis of Fostriecin via Asymmetric Alcohol-Mediated Carbonyl Allylation

Organic Letters, Год журнала: 2025, Номер unknown

Опубликована: Апрель 10, 2025

A formal synthesis of fostriecin via convergent assembly two fragments prepared asymmetric alcohol-mediated C-C coupling is described. One fragment made by the enantioselective iridium-catalyzed allylation an allylic alcohol mediated allyl acetate. The other ruthenium-catalyzed reductive syn-(α-alkoxy)allylation aldehyde alkoxyallene (where 2-propanol hydrogen source), representing first use this method in target-oriented synthesis. Metathetic union enables interception a late-stage compound that previously required 25 step (LLS) only 7 steps (LLS).

Язык: Английский

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