56294-19-0Relevant articles and documents
N-Ammonium Ylide Mediators for Electrochemical C-H Oxidation
Saito, Masato,Kawamata, Yu,Meanwell, Michael,Navratil, Rafael,Chiodi, Debora,Carlson, Ethan,Hu, Pengfei,Chen, Longrui,Udyavara, Sagar,Kingston, Cian,Tanwar, Mayank,Tyagi, Sameer,McKillican, Bruce P.,Gichinga, Moses G.,Schmidt, Michael A.,Eastgate, Martin D.,Lamberto, Massimiliano,He, Chi,Tang, Tianhua,Malapit, Christian A.,Sigman, Matthew S.,Minteer, Shelley D.,Neurock, Matthew,Baran, Phil S.
supporting information, p. 7859 - 7867 (2021/05/26)
The site-specific oxidation of strong C(sp3)-H bonds is of uncontested utility in organic synthesis. From simplifying access to metabolites and late-stage diversification of lead compounds to truncating retrosynthetic plans, there is a growing need for new reagents and methods for achieving such a transformation in both academic and industrial circles. One main drawback of current chemical reagents is the lack of diversity with regard to structure and reactivity that prevents a combinatorial approach for rapid screening to be employed. In that regard, directed evolution still holds the greatest promise for achieving complex C-H oxidations in a variety of complex settings. Herein we present a rationally designed platform that provides a step toward this challenge using N-ammonium ylides as electrochemically driven oxidants for site-specific, chemoselective C(sp3)-H oxidation. By taking a first-principles approach guided by computation, these new mediators were identified and rapidly expanded into a library using ubiquitous building blocks and trivial synthesis techniques. The ylide-based approach to C-H oxidation exhibits tunable selectivity that is often exclusive to this class of oxidants and can be applied to real-world problems in the agricultural and pharmaceutical sectors.
Pericyclic Umpolung. Reversal of Regioselectivity in the Diels-Alder Reaction
Shea, K. J.,Staab, Andrew J.,Zandi, Kathleen S.
, p. 2715 - 2718 (2007/10/02)
New methodology is reported which enables reversal of regiochemistry in the Diels-Alder reaction.Esterification of 2-(β-hydroxyethyl)dimethylsilyldienes with common dienophiles followed by type 2 intramolecular Diely-Alder reaction results in formation of a single regio- and stereoisomer.Oxidative cleavage of the cycloadduct produces a cyclohexanone with a substitution pattern opposite of that found in the analogous bimolecular cycloaddition reaction.
REACTION OF METHYL-SUBSTITUTED 7-CHLORO- AND 7,7-DICHLOROBICYCLOheptan-2-ones WITH SODIUM METHOXIDE AND THIOPHENOLATE
Kulinkovich, O. G.,Tishchenko, I. G.,Romashin, Yu. N.
, p. 81 - 85 (2007/10/02)
The reaction of exo-7-chloro-6-methylbicycloheptan-2-one, exo-7-chloro-4,4,6-trimethylbicycloheptan-2-one, 7,7-dichloro-6-methylbicyclo-heptan-2-one, and 7,7-dichloro-4,4,6-trimethylbicycloheptan-2-one with sodium methoxide takes place with opening of the cyclopropane ring and the formation of the corresponding 3-dimethoxymethyl- and 3-trimethoxymethylcyclohexanones.The reaction with sodium thiophenolate leads to the product from substitution of the exo-chlorine atom by the phenylthio group with retention of the three-membered ring.
Regioselectivity in the Intramolecular Carbon-Hydrogen Insertion in Metal-catalysed Decomposition of some cis-1-Methyl-3-arylcyclohexyl Diazomethyl Ketones. A Highly Efficient Homogeneous Nickel Catalyst for Carbenoid Insertion
Chakraborti, Asit K.,Ray, Jayanta K.,Kundu, Kalyan K.,Chakrabarty, Sephali,Mukherjee, Debabrata,Ghatak, Usha Ranjan
, p. 261 - 273 (2007/10/02)
The comparative effectiveness of a variety of copper catalysts and a few transition-metal chelates have been examined in the carbenoid decomposition of cis,cis-1,5-dimethyl-3-phenylcyclohexyl diazomethyl ketone (11),
Chemical Transformation of Terpenoids. VII. Syntheses of Chiral Segments, Key Building-Blocks for the Right Half of Taxane-Type Diterpenoids
Shibuya, Hirotaka,Tsujii, Shinji,Yamamoto, Yoshio,Miura, Hiromi,Kitagawa, Isao
, p. 3417 - 3427 (2007/10/02)
Two kinds of chiral segments, i.e. segment B-I (4) and segment B-II (5), which are potentially versatile building-blocks for construction of the right half of taxane-type diterpenoids, were synthesized from 3-methyl-2-cyclohexen-1-one (6) via optical reso
Thiazolidine derivatives and production thereof
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, (2008/06/13)
A thiazolidine derivative of the general formula, STR1 is a cyclohexane ring having an oxo or hydroxyl group as a substituent on any of the methylene groups constituting the ring and R is a hydrogen atom or a lower alkyl group having 1 to 4 carbon atoms,
gem-Dichlorocyclopropanes as Masked Esters: A Novel Synthesis of β-Methoxycarbonyl Aldehydes and Ketones
Banwell, Martin G.
, p. 1453 - 1454 (2007/10/02)
The carbonyl conjugated gem-dichlorocyclopropanes (1) react with sodium methoxide in methanol affording β-methoxycarbonyl aldehydes and ketones in high yield.
