85277-69-6

Upstream product

• 1929-29-9 3-(4-methoxyphenyl)propanoic acid 
• 115-11-7 isobutene 
• 104-92-7 1-bromo-4-methoxy-benzene 
• 540-88-5 acetic acid tert-butyl ester 
• 105-13-5 4-Methoxybenzyl alcohol 
• 1663-39-4 tert-Butyl acrylate 
• 123-11-5 4-methoxy-benzaldehyde 
• 86302-43-4 (tert-Butoxycarbonylmethylene)triphenylphosphorane 
• 696-62-8 para-iodoanisole 

Downstream Products

• 1049037-38-8 C₂₉H₃₇NO₆ 
• 1374134-18-5 tert-butyl 3-[4-methoxy-3-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-2,2-dimethylpropanoate 
• 1374134-20-9 tert-butyl 3-(4-methoxyphenyl)-2,2-dimethylpropanoate 
• 1374134-21-0 tert-butyl 3-(3-iodo-4-methoxyphenyl)-2,2-dimethylpropanoate 

Relevant academic research and scientific papers

Selective Construction of C?C and C=C Bonds by Manganese Catalyzed Coupling of Alcohols with Phosphorus Ylides

Herein, we report the manganese catalyzed coupling of alcohols with phosphorus ylides. The selectivity in the coupling of primary alcohols with phosphorus ylides to form carbon-carbon single (C?C) and carbon-carbon double (C=C) bonds can be controlled by the ligands. In the conversion of more challenging secondary alcohols with phosphorus ylides the selectivity towards the formation of C?C vs. C=C bonds can be controlled by the reaction conditions, namely the amount of base. The scope and limitations of the coupling reactions were thoroughly evaluated by the conversion of 21 alcohols and 15 ylides. Notably, compared to existing methods, which are based on precious metal complexes as catalysts, the present catalytic system is based on earth abundant manganese catalysts. The reaction can also be performed in a sequential one-pot reaction generating the phosphorus ylide in situ followed manganese catalyzed C?C and C=C bond formation. Mechanistic studies suggest that the C?C bond was generated via a borrowing hydrogen pathway and the C=C bond formation followed an acceptorless dehydrogenative coupling pathway. (Figure presented.).

Nickel-catalyzed: C-alkylation of thioamide, amides and esters by primary alcohols through a hydrogen autotransfer strategy

A simple catalyst of Ni(OAc)2 and P(t-Bu)3 enables selective C-alkylation of thioacetamides and primary acetamides with alcohols for the first time. Monoalkylation of thioamides, amides and t-butyl esters occurs in excellent yields (>95%). Mechanistic studies reveal that the reaction proceeds via a hydrogen autotransfer pathway. This journal is

Manganese-catalyzed direct C-C coupling of α-C-H bonds of amides and esters with alcohols: Via hydrogen autotransfer

Herein we report an efficient manganese-catalyzed C-alkylation of unactivated amides and tert-butyl acetate using alcohols as alkylating agents. This elegant approach exhibits a broad substrate scope providing the C-C coupled products of amides via a hydrogen auto-transfer strategy using aryl, heteroaryl, and aliphatic alcohols.

Bidentate Ru(II)-NC Complexes as Catalysts for α-Alkylation of Unactivated Amides and Esters

Five Ru(II)-NC complexes were tested as catalysts for α-alkylation of unactivated amides using alcohols as alkylating agents, and complex {(C5H4N)-(C6H4)}RuCl(CO)(PPh3)2 (1) showed the highest activity. With 0.5 mol% catalyst loading, a series of α-alkylated amides were isolated at 80 °C within 6 hours. Furthermore, under similar conditions, complex 1 was also active for α-alkylation of unactivated esters with alcohols, and the reaction time was shortened to 1.5 hours. The catalytic performance of 1 is comparable to the best reported catalyst.

Ni-Catalyzed Α-Alkylation of Unactivated Amides and Esters with Alcohols by Hydrogen Auto-Transfer Strategy

A transition-metal-catalyzed borrowing hydrogen/hydrogen auto-transfer strategy allows the utilization of feedstock alcohols as an alkylating partner, which avoids the formation of stoichiometric salt waste and enables a direct and benign approach for the construction of C-N and C?C bonds. In this study, a nickel-catalyzed α-alkylation of unactivated amides and ester (tert-butyl acetate) is carried out by using primary alcohols under mild conditions. This C?C bond-forming reaction is catalyzed by a new, molecularly defined nickel(II) NNN-pincer complex (0.1–1 mol %) and proceeds through hydrogen auto-transfer, thereby releasing water as the sole byproduct. In addition, N-alkylation of cyclic amides under Ni-catalytic conditions is demonstrated.

Sustainable Alkylation of Unactivated Esters and Amides with Alcohols Enabled by Manganese Catalysis

The first example of manganese-catalyzed C-alkylation of the carboxylic acid derivatives is reported. The bench-stable homogeneous manganese complex enables the transformation of the renewable alcohol and carboxylic acid derivative feedstock to higher value esters and amides. The reaction operates via hydrogen autotransfer and ideally produces water as the only side product. Importantly, aliphatic-, benzylic-, and heterocyclic-containing alcohols can be used as alkylating reagents, eliminating the need for mutagenic alkyl halides.

General and Mild Cobalt-Catalyzed C-Alkylation of Unactivated Amides and Esters with Alcohols

The borrowing hydrogen or hydrogen autotransfer methodology is an elegant and sustainable or green concept to construct carbon-carbon bonds. In this concept, alcohols, which can be obtained from barely used and indigestible biomass, such as lignocellulose, are employed as alkylating reagents. An especially challenging alkylation is that of unactivated esters and amides. Only noble metal catalysts based on iridium and ruthenium have been used to accomplish these reactions. Herein, we report on the first base metal-catalyzed α-alkylation of unactivated amides and esters by alcohols. Cobalt complexes stabilized with pincer ligands, recently developed in our laboratory, catalyze these reactions very efficiently. The precatalysts can be synthesized easily from commercially available starting materials on a multigram scale and are self-activating under the basic reaction conditions. This Co catalyst class is also able to mediate alkylation reactions of both esters and amides. In addition, we apply the methodology to synthesize ketones and to convert alcohols into aldehydes elongated by two carbon atoms.

A novel catalytic decarbonylative Heck-type reaction and conjugate addition of aldehydes to unsaturated carbonyl compounds

A novel rhodium-catalyzed decarbonylative reaction of aldehydes with unsaturated carbonyl compounds was discovered to generate Heck-type reaction product and conjugate addition product.

Suzuki-Miyaura cross-coupling of potassium trifluoroboratohomoenolates

Ketone-, ester-, and amide-containing potassium trifluoroboratohomoenolates were prepared in good to excellent yields from the corresponding unsaturated carbonyl compounds. They were shown to be effective coupling partners in the Suzuki-Miyaura reaction with a variety of electrophiles including electron-rich and electron-poor aryl bromides and -chlorides.