30189-87-8Relevant academic research and scientific papers
Mild and selective activation and substitution of strong aliphatic C-F bonds
Janjetovic, Mario,Tr?ff, Annika M.,Hilmersson, G?ran
, p. 3772 - 3777 (2015)
A procedure for chemoselectively manipulating the strong aliphatic C-F bond with direct transformation into a C-N bond under mild conditions is reported. The activation and subsequent substitution of primary alkyl fluorides is mediated by La[N(SiMe3)2]3, and results in high to excellent yields of tertiary amines. The methodology displays high selectivity towards the C(sp3)-F bond, and a variety of secondary amines are applicable as nucleophiles. Mechanistic investigations reveal a reaction that is first order with respect to [La[N(SiMe3)2]3], [R1R2NH], and [alkyl fluoride], and a 6-membered cyclic transition state is proposed. In addition, 1H NMR spectroscopy shows that La[N(SiMe3)2]3 is the active species involved in the substitution and that protonolysis of the amine, yielding La[NR1R2]3, lowers the reactivity.
Overcoming solid handling issues in continuous flow substitution reactions through ionic liquid formation
Kashani, Saeed,Sullivan, Ryan J.,Andersen, Mads,Newman, Stephen G.
supporting information, p. 1748 - 1753 (2018/04/30)
Substitutions such as acylations, arylations, and alkylations are some of the most commonly run reactions for building complex molecules. However, the requirement of a stoichiometric base to scavange acid by-products creates significant challenges when operating in continuous flow due to solid handling issues associated with precipitating base·HX salts. We present a general and simple strategy to overcome these solid handling issues through the use of acid scavenging organic bases that generate low- to moderate-melting ionic liquids upon protonation. The application of these bases towards the most commonly run substitutions are demonstrated, enabling reactions to be run in flow without requiring additional equipment, specific solvents, or dilute reaction conditions to prevent clogging.
Synthesis of 1,3-Amino Alcohols, 1,3-Diols, Amines, and Carboxylic Acids from Terminal Alkynes
Zeng, Mingshuo,Herzon, Seth B.
, p. 8604 - 8618 (2015/09/15)
The half-sandwich ruthenium complexes 1-3 activate terminal alkynes toward anti-Markovnikov hydration and reductive hydration under mild conditions. These reactions are believed to proceed via addition of water to metal vinylidene intermediates (4). The functionalization of propargylic alcohols by metal vinylidene pathways is challenging owing to decomposition of the starting material and catalytic intermediates. Here we show that catalyst 2 can be employed to convert propargylic alcohols to 1,3-diols in high yield and with retention of stereochemistry at the propargylic position. The method is also amenable to propargylic amine derivatives, thereby establishing a route to enantioenriched 1,3-amino alcohol products. We also report the development of formal anti-Markovnikov reductive amination and oxidative hydration reactions to access linear amines and carboxylic acids, respectively, from terminal alkynes. This chemistry expands the scope of products that can be prepared from terminal alkynes by practical and high-yielding metal-catalyzed methods.
Hydroborations, reductions and reductive iodinations using BHI2:N(C2H5)2Ph complex
Kishan Reddy,Periasamy
, p. 8329 - 8336 (2007/10/02)
The BHI2:N(C2H5)2Ph complex, prepared by the reaction of BH3:N(C2H5)2Ph with I2, is useful for hydroboration of alkenes, reduction of amides, iodination of alcohols, reductive iodination of carboxylic acids, aldehydes and ketones. Selective hydroboration of monosubstituted olefin over disubstituted olefinic moiety and terminal olefin over internal alkyne moiety have been achieved using this reagent. Carboxylic esters and nitriles are not affected by this reagent. Selective hydroboration of 1-alkenes and selective reductive iodination of cyclohexanone are achieved in the presence of ester and nitrile functional groups.
