180295-28-7Relevant academic research and scientific papers
Tweaking copper hydride (CuH) for synthetic gain. A practical, one-pot conversion of dialkyl ketones to reduced trialkylsilyl ether derivatives
Lipshutz, Bruce H.,Caires, Christopher C.,Kuipers, Peter,Chrisman, Will
, p. 3085 - 3088 (2003)
(Matrix presented) Variations in the reagents and stoichiometries used to generate CuH in situ, as well as the nature of the ligands present, have led to a very efficient and inexpensive method for effecting hydrosilylations of dialkyl ketones.
Nickel-Catalyzed Decarboxylative Coupling of Redox-Active Esters with Aliphatic Aldehydes
Xiao, Jichao,Li, Zhenning,Montgomery, John
supporting information, p. 21234 - 21240 (2021/12/27)
The addition of alkyl fragments to aliphatic aldehydes is a highly desirable transformation for fragment couplings, yet existing methods come with operational challenges related to the basicity and instability of the nucleophilic reagents commonly employed. We report herein that nickel catalysis using a readily available bioxazoline (BiOx) ligand can catalyze the reductive coupling of redox-active esters with aliphatic aldehydes using zinc metal as the reducing agent to deliver silyl-protected secondary alcohols. This protocol is operationally simple, proceeds under mild conditions, and tolerates a variety of functional groups. Initial mechanistic studies suggest a radical chain pathway. Additionally, alkyl tosylates and epoxides are suitable alkyl precursors to this transformation providing a versatile suite of catalytic reactions for the functionalization of aliphatic aldehydes.
Synergistic Catalysis by Br?nsted Acid/Carbodicarbene Mimicking Frustrated Lewis Pair-Like Reactivity
Bai, Yuna,Chan, Yi-Chen,Chen, Hsing-Yin,Chen, Hsuan-Ying,Chen, Wen-Ching,Li, Chen-Yu,Ong, Tiow-Gan,Tseng, Mei-Chun,Wu, Ying-Yann,Yap, Glenn P. A.,Zhao, Lili
supporting information, p. 19949 - 19956 (2021/08/03)
Carbodicarbene (CDC), unique carbenic entities bearing two lone pairs of electrons are well-known for their strong Lewis basicity. We demonstrate herein, upon introducing a weak Br?nsted acid benzyl alcohol (BnOH) as a co-modulator, CDC is remolded into a Frustrated Lewis Pair (FLP)-like reactivity. DFT calculation and experimental evidence show BnOH loosely interacting with the binding pocket of CDC via H-bonding and π-π stacking. Four distinct reactions in nature were deployed to demonstrate the viability of proof-of-concept as synergistic FLP/Modulator (CDC/BnOH), demonstrating enhanced catalytic reactivity in cyclotrimerization of isocyanate, polymerization process for L-lactide (LA), methyl methacrylate (MMA) and dehydrosilylation of alcohols. Importantly, the catalytic reactivity of carbodicarbene is uniquely distinct from conventional NHC which relies on only single chemical feature of nucleophilicity. This finding also provides a new spin in diversifying FLP reactivity with co-modulator or co-catalyst.
Carbonyl and olefin hydrosilylation mediated by an air-stable phosphorus(iii) dication under mild conditions
Andrews, Ryan J.,Chitnis, Saurabh S.,Stephan, Douglas W.
supporting information, p. 5599 - 5602 (2019/05/21)
The readily-accessible, air-stable Lewis acid [(terpy)PPh][B(C6F5)4]21 is shown to mediate the hydrosilylation of aldehydes, ketones, and olefins. The utility and mechanism of these hydrosilylations are considered.
A Versatile Iridium(III) Metallacycle Catalyst for the Effective Hydrosilylation of Carbonyl and Carboxylic Acid Derivatives
Corre, Yann,Rysak, Vincent,Trivelli, Xavier,Agbossou-Niedercorn, Francine,Michon, Christophe
supporting information, p. 4820 - 4826 (2017/09/07)
A versatile iridium(III) metallacycle catalysed rapidly and selectively the reduction of a large array of challenging esters and carboxylic acids as well as various ketones and aldehydes. The reactions proceeded in high yields at room temperature by hydrosilylation followed by desilylation. Although the reactions of various aldehydes and ketones resulted exclusively in alcohols, the hydrosilylation of esters led to alcohols or ethers, depending on the type of substrate. Regarding the carboxylic acids, again the nature of the reagent controlled the outcome of the hydrosilylation reaction, either alcohols or aldehydes being formed.
Activation of silylphosphines by diethyl azodicarboxylate: Novel silylation of alcohols
Hayashi, Minoru,Matsuura, Yutaka,Watanabe, Yutaka
, p. 1409 - 1411 (2007/10/03)
A novel activation mode of silylphosphines and an application of that to silylation of alcohols were described. Silylphosphines were found to be instantly activated by means of DEAD and PPTS to form reactive silyl cation equivalents. By using the activate
