10094-36-7Relevant articles and documents
A new coupling reaction of alkyl iodides with α,β-unsaturated esters using Ni2B(cat.)-BER in methanol
Sim, Tae Bo,Choi, Jaesung,Yoon, Nung Min
, p. 3137 - 3140 (1996)
Alkyl iodides can be coupled with α,β-unsaturated esters using Ni2B(0.05-0.2 eq)-BER(3 eq) in methanol at room temperature. Products (68-95%) are conveniently isolated, simply filtering the resin and evaporating the excess enoates and methanol.
An unprecedented and highly chemoselective esterification method
Lee, Shih-Yuan Adam,Yang, Hui-Chun,Su, Feng-Yih
, p. 301 - 303 (2001)
A series of carboxylic acids was transformed to their corresponding methyl esters under CBr4/CH3OH (0.05 eq., 5 ml) reaction conditions. The rate of esterification is decreased with increasing bulkiness of the alcohol. Chemoselectivity can be achieved between phenylacetic and benzoic acids, sp3-C and sp2-C acids as well as between sp3-C and sp-C tethered carboxylic acids.
Cobalt-catalyzed reductive coupling of saturated alkyl halides with activated alkenes
Shukla, Paritosh,Hsu, Yun-Chu,Cheng, Chien-Hong
, p. 655 - 658 (2006)
An efficient cobalt-catalyzed reductive coupling reaction of alkyl halides with electron-withdrawing alkenes (CH2=CR1EWG, EWG = electron-withdrawing group) in the presence of water and zinc powder in acetonitrile to give the corresponding Michael-type addition product (RCH 2CR1EWG) was described. The methodology is versatile such that unactivated primary, secondary, and tertiary alkyl bromides and iodides and various conjugated alkenes including acrylates, acrylonitrile, methyl vinyl ketone, and vinyl sulfone all successfully participate in this coupling reaction. For the alkyl halides used in the reaction, the iodides generally gave heller yields compared to those of the corresponding bromides. It is a unique method employing CoI2dppe, zinc, and alkyl halides, affording conjugate addition products in high yields. Mechanistically, the reaction appears to follow an oxidative addition driven route rather than the previously reported radical route.
Reductive bromine atom-transfer reaction
Sumino, Shuhei,Fusano, Akira,Ryu, Ilhyong
, p. 2826 - 2829 (2013)
Atom-transfer radical (ATR) reactions of alkenes with R-X usually give products having new C-C and C-X bonds at the adjacent carbons. However, when the reaction was carried out under irradiation using a low-pressure Hg lamp, addition/reduction products were obtained in good yield. Hydrogen bromide, formed by H-abstraction of a bromine radical from alkenes, is likely to play a key role in the reductive ATR reaction.
REACTIONS OF ORGANIC HALIDES WITH OLEFINS UNDER Ni0-CATALYSIS. FORMAL ADDITION OF HYDROCARBONS TO CC-DOUBLE BONDS
Sustmann, Reiner,Hopp, Peter,Holl, Peter
, p. 689 - 692 (1989)
The reaction of various types of organic halides with electron deficient olefins under the influence of NiCl2 x 6 H2O in the presence of zinc and pyridine leads to formal addition products of hydrocarbons to CC-double bonds in good yield.
BIS(TRI-n-BUTYLSTANNYL)BENZOPINACOLATE: PREPARATION AND USE AS A MEDIATOR OF INTERMOLECULAR FREE RADICAL REACTIONS
Hart, David J.,Krishnamurthy, Ramanarayanan,Pook, Lori M.,Seely, Franklin L.
, p. 7819 - 7822 (1993)
Bis(tri-n-butylstannyl)benzopinacolinate (2) serves as a thermal source of tri-n-butylstannyl radicals and mediates intermolecular coupling of selected alkyl halides to O-benzylformaldoxime and electron deficient olefins.A free radical non-chain mechanism is proposed for these reactions.
Electrochemical Tandem Olefination and Hydrogenation Reaction with Ammonia
Zhang, Xiaofeng,Jiang, Runze,Cheng, Xu
supporting information, p. 16016 - 16025 (2021/08/24)
An electrochemical Horner-Wadsworth-Emmons/hydrogenation tandem reaction was achieved using ammonia as electron and proton donors. The reaction could give two-carbon-elongated ester and nitrile from aldehyde or ketones directly. This reaction could proceed with a catalytic amount of base or even without a base. The ammonia provides both the electron and proton for this tandem reaction and enables the catalyst-free hydrogenation of an α,β-unsaturated HWE intermediate. More than 40 examples were reported, and functional groups, including heterocycles and hydroxyl, were tolerated.
Aromatic compound hydrogenation and hydrodeoxygenation method and application thereof
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Paragraph 0094-0096; 0098; 0100-0104, (2021/05/29)
The invention belongs to the technical field of medicines, and discloses an aromatic compound hydrogenation and hydrodeoxygenation method under mild conditions and application of the method in hydrogenation and hydrodeoxygenation reactions of the aromatic compounds and related mixtures. Specifically, the method comprises the following steps: contacting the aromatic compound or a mixture containing the aromatic compound with a catalyst and hydrogen with proper pressure in a solvent under a proper temperature condition, and reacting the hydrogen, the solvent and the aromatic compound under the action of the catalyst to obtain a corresponding hydrogenation product or/and a hydrodeoxygenation product without an oxygen-containing substituent group. The invention also discloses specific implementation conditions of the method and an aromatic compound structure type applicable to the method. The hydrogenation and hydrodeoxygenation reaction method used in the invention has the advantages of mild reaction conditions, high hydrodeoxygenation efficiency, wide substrate applicability, convenient post-treatment, and good laboratory and industrial application prospects.
Copper-Catalyzed Alkoxycarbonylation of Alkyl Iodides for the Synthesis of Aliphatic Esters: Hydrogen Makes the Difference
Geng, Hui-Qing,Wu, Xiao-Feng
, p. 8062 - 8066 (2021/10/25)
A copper-catalyzed alkoxycarbonylation transformation of unactivated alkyl iodides has been developed. Various alkyl iodides can be converted into the corresponding tert-butyl esters in good yields. NaOtBu acts as both a nucleophile and a base. Moreover, other types of aliphatic esters can also be obtained in moderated yields if extra alcohols are added. Both primary and secondary alkyl alcohols can react successfully.
Copper catalyzed C(sp3)-H bond alkylation via photoinduced ligand-to-metal charge transfer
Treacy, Sean M.,Rovis, Tomislav
supporting information, p. 2729 - 2735 (2021/03/01)
Utilizing catalytic CuCl2 we report the functionalization of numerous feedstock chemicals via the coupling of unactivated C(sp3)-H bonds with electron-deficient olefins. The active cuprate catalyst undergoes Ligand-to-Metal Charge Transfer (LMCT) to enable the generation of a chlorine radical which acts as a powerful hydrogen atom transfer reagent capable of abstracting strong electron-rich C(sp3)-H bonds. Of note is that the chlorocuprate catalyst is an exceedingly mild oxidant (0.5 V vs SCE) and that a proposed protodemetalation mechanism offers a broad scope of electron-deficient olefins, offering high diastereoselectivity in the case of endocyclic alkenes. The coupling of chlorine radical generation with Cu reduction through LMCT enables the generation of a highly active HAT reagent in an operationally simple and atom economical protocol.
