Metal catalyst-free N-Allylation/alkylation of Imidazole and Benzimidazole with Morita-Baylis-Hillman (MBH) alcohols and acetates DOI Creative Commons
Olfa Mhasni, Jalloul Bouajila, Farhat Rezgui

и другие.

Опубликована: Май 23, 2023

A highly a-regioselective N -nucleophilic allylic substitutions of cyclic MBH alcohols and acetates with imidazole or benzimidazole, in toluene at reflux an azeotropic distillation, was successfully carried out no catalysts additives, affording the corresponding -substituted derivatives good yields. On other hand, refluxing methanol, aza-Michael additions onto acyclic performed using DABCO as additive, leading to 1,4-adducts 70-84%

Язык: Английский

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

Adam Cook,

Stephen G. Newman

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

Процитировано

39
Copper-catalyzed regio- and stereo-selective hydrosilylation of terminal allenes to access (E)-allylsilanes DOI Creative Commons
Shaowei Chen,

Xiaoqian He,

Yi Jin

и другие.

Nature Communications, Год журнала: 2022, Номер 13(1)

Опубликована: Июнь 27, 2022

Abstract Regioselectivity and stereoselectivity control in hydrosilylation of terminal allenes is challeging. Although the selective synthesis vinylsilanes, branched allylsilanes or linear ( Z )-allylsilanes have been achieved, transition-metal catalyzed to access E )-allylsilane difficult. Herein, we report a copper-catalyzed reaction under mild conditions. The shows broad substrate scope, representing an efficient method prepare trisubstituted through can also be applied disubstituted )-allylsilanes. mechanism study reveals that -selectivity kinetically controlled by catalyst but not thermodynamically isomerization )-isomer.

Язык: Английский

Процитировано

32
Photoredox/Nickel-Catalyzed Diastereoselective Allylation of Aldehydes with Morita–Baylis–Hillman Adducts DOI Creative Commons
F. Calogero, Emanuele Pinosa, Andrea Gualandi

и другие.

ACS Catalysis, Год журнала: 2025, Номер 15(10), С. 8303 - 8316

Опубликована: Май 2, 2025

A practical diastereoselective photoredox nickel-mediated allylation of aliphatic and aromatic aldehydes with Morita-Baylis-Hillman (MBH) acetates is reported here. The reaction proceeds under visible-light irradiation using MBH derivatives, which are easily prepared from inexpensive available starting materials, affording functionalized alcohols as a single diastereoisomer (>20:1 for the syn diastereoisomer). popular organic dye 3DPAFIPN used photocatalyst in combination Hantzsch ester presence catalytic amount stable nickel complexes o-phenanthroline ligand. shows broad scope, avoiding use Ni(0), well stoichiometric metal reductants such Zn Mn. relevance was confirmed by products rapid access to α-methylene-β-lactones, useful intermediates synthesis natural or biologically active relevant products. DFT calculations suggest that allyl acetate-coordinated Ni(0) species plays role catalyst cycle operates through Ni(0)-Ni(II)-Ni(I)-Ni(0) pathway.

Язык: Английский

Процитировано

1
Nickel-Catalyzed Asymmetric Allylic Alkylation of β-Dicarbonyl Compounds via C–C Bond Activation of 2-Allylated Cyclic 1,3-Diketones DOI
Kosuke Higashida,

Valentin Smaïl,

Haruki Nagae

и другие.

ACS Catalysis, Год журнала: 2023, Номер 13(3), С. 2156 - 2161

Опубликована: Янв. 25, 2023

The asymmetric allylic alkylation (AAA) reaction using less reactive, stable sources is challenging. We achieved a nickel(0)-catalyzed AAA of β-dicarbonyl compounds under ambient conditions through unstrained C–C bond activation 2-allylated 2-methylcyclohexane-1,3-dione derivatives to afford the corresponding quaternary chiral in high yield with enantioselectivity. proceeded almost irreversibly due low solubility side-product, 2-methylcyclohexane-1,3-dione. Control experiments and DFT calculations allowed for elucidating mechanism Ni(0)-(S)-tol-MeO-BIPHEP catalyst system; turnover limiting step formation, reverse requires 7.6 kcal mol–1 higher energy than forward reaction.

Язык: Английский

Процитировано

10
New Morita-Baylis-Hillman (MBH) phosphonium salts from alcohols to the synthesis of 2-alkenyl- and 2-alkylidenecyclohexenones DOI
Haïtham Elleuch, Dhouha Msalbi, Olfa Mhasni

и другие.

Journal of Molecular Structure, Год журнала: 2023, Номер 1286, С. 135532 - 135532

Опубликована: Апрель 12, 2023

Язык: Английский

Процитировано

6
Asymmetric organocatalytic Morita−Baylis−Hillman reaction and asymmetric organocatalytic transformations of Morita−Baylis−Hillman adducts. An update DOI

Hélène Pellissier

Tetrahedron, Год журнала: 2024, Номер 172, С. 134435 - 134435

Опубликована: Дек. 23, 2024

Язык: Английский

Процитировано

1
Allylic C(sp3)−C(sp3) Bond Formation Through Pd‐Catalyzed C(sp3)−H Activation of Alkenes and 1,4‐Dienes DOI
Jacques Мuzart

Advanced Synthesis & Catalysis, Год журнала: 2022, Номер 364(14), С. 2268 - 2288

Опубликована: Май 10, 2022

Abstract This review highlights the allylic C−H alkylation of alkenes (AA H ) with nucleophiles under Pd 0 or II catalysis and achiral chiral conditions. The η 3 ‐allylpalladium intermediates these reactions are formed from cleavage an hydrogen which becomes a leaving group, like acetate moiety allyl acetates during classical Tsuji‐Trost procedure. Most cross‐dehydrogenative‐couplings require quinones as key components; they may play role ligand, proton trap oxidant. Efficient asymmetric alkylations (AAA ’s) have been performed. diversity procedures, their limitation application in synthesis underlined well proposed mechanisms with, some cases, personal comments. data grouped according to reaction magnified image

Язык: Английский

Процитировано

5
An efficient one-step synthesis of a new series of mutifunctional olefins and direct hydroxymethylation of α-substituted β-keto esters DOI
Olfa Mhasni, Julien Legros, Farhat Rezgui

и другие.

Synthetic Communications, Год журнала: 2024, Номер unknown, С. 1 - 12

Опубликована: Сен. 13, 2024

Язык: Английский

Процитировано

0
Metal catalyst-free N-allylation/alkylation of imidazole and benzimidazole with Morita–Baylis–Hillman (MBH) alcohols and acetates DOI Creative Commons
Olfa Mhasni, Jalloul Bouajila, Farhat Rezgui

и другие.

Beilstein Journal of Organic Chemistry, Год журнала: 2023, Номер 19, С. 1251 - 1258

Опубликована: Сен. 1, 2023

A highly α-regioselective N-nucleophilic allylic substitution of cyclic MBH alcohols and acetates with imidazole or benzimidazole, in toluene at reflux an azeotropic distillation, was successfully carried out no catalysts additives, affording the corresponding N-substituted derivatives good yields. On other hand, refluxing methanol, aza-Michael addition onto acyclic performed using DABCO as additive, leading to 1,4-adducts 70–84%

Язык: Английский

Процитировано

0
Metal catalyst-free N-Allylation/alkylation of Imidazole and Benzimidazole with Morita-Baylis-Hillman (MBH) alcohols and acetates DOI Creative Commons
Olfa Mhasni, Jalloul Bouajila, Farhat Rezgui

и другие.

Опубликована: Май 23, 2023

A highly a-regioselective N -nucleophilic allylic substitutions of cyclic MBH alcohols and acetates with imidazole or benzimidazole, in toluene at reflux an azeotropic distillation, was successfully carried out no catalysts additives, affording the corresponding -substituted derivatives good yields. On other hand, refluxing methanol, aza-Michael additions onto acyclic performed using DABCO as additive, leading to 1,4-adducts 70-84%

Язык: Английский

Процитировано

0