Direct Deprotonative Functionalization of α,α‐Difluoromethyl Ketones using a Catalytic Organosuperbase
نویسندگان
چکیده
The deprotonative functionalization of α,α-difluoromethyl ketones is described herein. Using a catalytic organosuperbase and silane additive, the corresponding difluoroenolate could be generated trapped with aldehydes to deliver various α,α-difluoro-β-hydroxy in high yields. This new strategy tolerates numerous functional groups represents access by direct deprotonation difluoromethyl unit. diastereoselective version reaction was also investigated d.r. up 93 : 7. Several transformations were performed demonstrate synthetic potential these ketones. In addition, this method has been extended use other electrophiles such as imines chalcogen derivatives, sulfoxide nucleophile, thus leading diversity difluoromethylene compounds.
منابع مشابه
Metal-free deprotonative functionalization of heteroaromatics using organic superbase catalyst.
Metal-free deprotonative functionalization of heteroaromatic compounds was achieved using an organic superbase catalyst; an organosilicon additive such as trimethylsilylpropyne was employed for activating the catalytic cycle of 1,2-addition to carbonyl compounds.
متن کامل[A novel deprotonative functionalization of aromatics with phosphazene base].
A novel type of deprotonative functionalization of aromatics was accomplished with a phosphazene base (t-Bu-P4 base). For various nitrogen heteroaromatics and benzene derivatives, deprotonative 1,2-additions proceeded with the t-Bu-P4 base and ZnI(2) as an additive in the presence of carbonyl compounds. The t-Bu-P4 base has both extremely strong Brønsted basicity and less nucleophilicity due to...
متن کاملDirect β-functionalization of cyclic ketones with aryl ketones via the merger of photoredox and organocatalysis.
The direct β-coupling of cyclic ketones with aryl ketones has been achieved via the synergistic combination of photoredox catalysis and organocatalysis. Diaryl oxymethyl or aryl-alkyl oxymethyl radicals, transiently generated via single-electron reduction of ketone precursors, readily merge with β-enaminyl radical species, generated by photon-induced enamine oxidation, to produce γ-hydroxyketon...
متن کاملCatalytic enantioselective direct Michael additions of ketones to alkylidene malonates
Enantioselective direct Michael additions of ketones using (S)-1-(2-pyrrolidinylmethyl)-pyrrolidine as a catalyst are described. Michael adducts with up to 91% e.e. were obtained by the reaction of alkylidene malonates with simple unactivated ketones under mild reaction conditions. © 2001 Elsevier Science Ltd. All rights reserved. An increasing demand for optically active compounds has stimulat...
متن کاملCatalytic asymmetric alkylation of ketones using organometallic reagents.
The catalytic asymmetric synthesis of tertiary alcohols by the addition of organometallic reagents to ketones is of central importance in organic chemistry. The resulting quaternary stereocentres are difficult to prepare selectively by other means despite their widespread occurrence in natural products and pharmaceuticals. Over the past few years, several seminal reports on the formation of chi...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
ژورنال
عنوان ژورنال: Angewandte Chemie
سال: 2023
ISSN: ['1521-3773', '1433-7851', '0570-0833']
DOI: https://doi.org/10.1002/ange.202215899