- Synergistic Activation of Amides and Hydrocarbons for Direct C(sp3)–H Acylation Enabled by Metallaphotoredox Catalysis
-
The utilizations of omnipresent, thermodynamically stable amides and aliphatic C(sp3)?H bonds for various functionalizations are ongoing challenges in catalysis. In particular, the direct coupling between the two functional groups has not been realized. Here, we report the synergistic activation of the two challenging bonds, the amide C?N and unactivated aliphatic C(sp3)?H, via metallaphotoredox catalysis to directly acylate aliphatic C?H bonds utilizing amides as stable and readily accessible acyl surrogates. N-acylsuccinimides served as efficient acyl reagents for the streamlined synthesis of synthetically useful ketones from simple C(sp3)?H substrates. Detailed mechanistic investigations using both computational and experimental mechanistic studies were performed to construct a detailed and complete catalytic cycle. The origin of the superior reactivity of the N-acylsuccinimides over other more reactive acyl sources such as acyl chlorides was found to be an uncommon reaction pathway which commences with C?H activation prior to oxidative addition of the acyl substrate.
- Baik, Mu-Hyun,Choi, Seulhui,Hong, Soon Hyeok,Lee, Geun Seok,Won, Joonghee
-
p. 16933 - 16942
(2020/08/03)
-
- Benzothiazolines as radical transfer reagents: Hydroalkylation and hydroacylation of alkenes by radical generation under photoirradiation conditions
-
Novel radical transfer reagents under photoirradiation conditions were developed by the use of benzothiazoline derivatives. These reagents enabled both hydroalkylation and hydroacylation of alkenes under neutral conditions at ambient temperature without a
- Uchikura, Tatsuhiro,Moriyama, Kaworuko,Toda, Mitsuhiro,Mouri, Toshiki,Ibá?ez, Ignacio,Akiyama, Takahiko
-
p. 11171 - 11174
(2019/09/30)
-
- Visible-Light-Promoted Synthesis of 1,4-Dicarbonyl Compounds via Conjugate Addition of Aroyl Chlorides
-
A facile visible-light photocatalytic conjugate addition to prepare 1,4-dicarbonyl compounds has been developed by employing readily available aroyl chlorides as aryl radical sources. This operationally simple method shows a broad scope with regard to both aroyl chlorides and Michael acceptors. As a result, a variety of 1,4-diketones were efficiently synthesized in moderate to good yields.
- Wang, Chao-Ming,Song, Dan,Xia, Peng-Ju,Wang, Jing,Xiang, Hao-Yue,Yang, Hua
-
supporting information
p. 271 - 274
(2018/01/27)
-
- Decarboxylative 1,4-Addition of α-Oxocarboxylic Acids with Michael Acceptors Enabled by Photoredox Catalysis
-
Enabled by iridium photoredox catalysis, 2-oxo-2-(hetero)arylacetic acids were decarboxylatively added to various Michael acceptors including α,β-unsaturated ester, ketone, amide, aldehyde, nitrile, and sulfone at room temperature. The reaction presents a new type of acyl Michael addition using stable and easily accessible carboxylic acid to formally generate acyl anion through photoredox-catalyzed radical decarboxylation.
- Wang, Guang-Zu,Shang, Rui,Cheng, Wan-Min,Fu, Yao
-
supporting information
p. 4830 - 4833
(2015/10/12)
-
- THERAPEUTIC AGENT FOR DIABETES
-
A therapeutic agent for diabetes, which comprises a compound of the formula [I] wherein Xis a group of the formula wherein R4and R5are the same or different and each is a hydrogen atom, an optionally substituted alkyl having 1 to 5 carbon atoms and the like, and R6is a hydrogen atom or an amino-protecting group; R1is an optionally substituted alkyl having 1 to 5 carbon atoms, an optionally substituted alkenyl having 2 to 6 carbon atoms and the like, R2is a hydrogen atom, an optionally substituted alkyl having 1 to 5 carbon atoms and the like, R2' is a hydrogen atom, and R3is an optionally substituted alkyl having 1 to 5 carbon atoms and the like, a prodrug thereof, a pharmaceutically acceptable salt thereof, a hydrate thereof and a solvate thereof. The compound of the present invention shows superior blood sugar decreasing action on the state of hyperglycemia, but does not affect the blood sugar when it is in the normal range or in the hypoglycemic state, which means that it is free of serious side effects such as hypoglycemia. Therefore, the compound of the present invention is useful as a therapeutic drug for diabetes and also useful as a preventive of the chronic complications of diabetes.
- -
-
-
- Samarium diiodide-mediated pinacolization of diketones - II. Synthesis of polycyclic frameworks containing a cyclobutane-1,2-diol and a cyclopentane-1,2-diol
-
The title reaction has been applied to the synthesis of a variety of polycyclic networks. Scope and limitations of the procedure are evaluated.
- Nowitzki, Olaf,Muennich, Ira,Stucke, Holger,Hoffmann
-
p. 11799 - 11810
(2007/10/03)
-
- ACYLSILANE-MEDIATED NUCLEOPHILIC ACYLATION OF α,β-UNSATURATED CARBONYL DERIVATIVES
-
A number of 1,4-diketones and of γ-keto esters can be prepared regiospecifically under mild conditions by employing a TBACN-catalysed Michael addition of acylsilanes to α,β-unsaturated carbonyl derivatives.
- degl'Innocenti, Alessandro,Ricci, Alfredo,Mordini, Alessandro,Reginato, Gianna,Colotta, Vittoria
-
p. 645 - 648
(2007/10/02)
-
- AMINONITRILE AND CYANOHYDRIN ETHERS AS BENZOYL ANION EQUIVALENTS IN CONJUGATE ADDITIONS TO SUBSTITUTED α CYCLENONES : COMPARATIVE SYNTHETIC POTENTIALITIES
-
Lithiated aminonitrile 1a and cyanohydrin ether 2a are good nucleophilic benzoyl equivalents in conjugate addition to α cyclenones. 1a is more sensitive to β substitution of the cyclenone than 2a, as in THF it does not react with 3-methyl substituted cycl
- Zervos, Michel,Wartski, Lya,Seyden-Penne, Jacqueline
-
p. 4963 - 4974
(2007/10/02)
-
- THE PREPARATION OF 1,4-DICARBONYL COMPOUNDS BY PHOTOREACTION OF KETONES IN THE PRESENCE OF OXIDANTS
-
Phenyl alkyl ketones were photo-irradiated in the presence of Cr(VI) or Mn(VII) oxidants to yield 1,4-dicarbonyl compounds regiospecifically while 2-octanone gave a regioisomeric mixture of 2,5-, 2,6-, and 2,7-octadiones.
- Mitani, Michiharu,Tamada, Mamoru,Uehara, Shin-ichi,Koyama, Kikuhiko
-
p. 2805 - 2808
(2007/10/02)
-
- ADDITION CONJUGUEE D'AMINONITRILES, EQUIVALENTS DE BENZOYLE, AUX CYCLENONES. QUELQUES EXEMPLES DE SYNTHESES STEREOSELECTIVES DE CYCLANONES 2,3-DISUBSTITUEES CIS.
-
Conjugate addition of benzoyl anion equivalents to unsubstituted and 2-substituted cyclenones is proved in some cases to be highly stereoselective.Cis 2-methyl 3-benzoyl cyclanones are obtained with excellent yields.
- Zervos, M.,Wartski, L.
-
p. 4641 - 4644
(2007/10/02)
-