22875-82-7Relevant articles and documents
Binuclear Pd(I)-Pd(I) Catalysis Assisted by Iodide Ligands for Selective Hydroformylation of Alkenes and Alkynes
Zhang, Yang,Torker, Sebastian,Sigrist, Michel,Bregovi?, Nikola,Dydio, Pawe?
supporting information, p. 18251 - 18265 (2020/11/02)
Since its discovery in 1938, hydroformylation has been thoroughly investigated and broadly applied in industry (>107 metric ton yearly). However, the ability to precisely control its regioselectivity with well-established Rh- or Co-catalysts has thus far proven elusive, thereby limiting access to many synthetically valuable aldehydes. Pd-catalysts represent an appealing alternative, yet their use remains sparse due to undesired side-processes. Here, we report a highly selective and exceptionally active catalyst system that is driven by a novel activation strategy and features a unique Pd(I)-Pd(I) mechanism, involving an iodide-assisted binuclear step to release the product. This method enables β-selective hydroformylation of a large range of alkenes and alkynes, including sensitive starting materials. Its utility is demonstrated in the synthesis of antiobesity drug Rimonabant and anti-HIV agent PNU-32945. In a broader context, the new mechanistic understanding enables the development of other carbonylation reactions of high importance to chemical industry.
Mild Iridium-Catalysed Isomerization of Epoxides. Computational Insights and Application to the Synthesis of β-Alkyl Amines
Cabré, Albert,Cabezas-Giménez, Juanjo,Sciortino, Giuseppe,Ujaque, Gregori,Verdaguer, Xavier,Lledós, Agustí,Riera, Antoni
supporting information, p. 3624 - 3631 (2019/07/10)
The isomerization of epoxides to aldehydes using the readily available Crabtree's reagent is described. The aldehydes were transformed into synthetically useful amines by a one-pot reductive amination using pyrrolidine as imine-formation catalyst. The reactions worked with low catalyst loadings in very mild conditions. The procedure is operationally simple and tolerates a wide range of functional groups. A DFT study of its mechanism is presented showing that the isomerization takes place via an iridium hydride mechanism with a low energy barrier, in agreement with the mild reaction conditions. (Figure presented.).
SYNTHESIZING METHOD OF α-TERTIARY ARYL KETONE
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Paragraph 0069; 0070; 0076; 0077, (2017/08/02)
The present invention relates to a synthesizing method of alpha-tertiary aryl ketone. The synthesizing method of alpha-tertiary aryl ketone synthesizes alpha-tertiary aryl ketone by making aldehyde react with aryldiazoalkanes under a chiral boron Lewis ac
Catalytic Asymmetric Formal Insertion of Aryldiazoalkanes into the C-H Bond of Aldehydes: Synthesis of Enantioenriched Acyclic α-Tertiary Aryl Ketones
Kang, Byung Chul,Nam, Dong Guk,Hwang, Geum-Sook,Ryu, Do Hyun
supporting information, p. 4810 - 4813 (2015/10/12)
A novel, catalytic enantioselective route to synthesize a variety of α-tertiary aryl ketones via a boron Lewis acid promoted formal insertion of aryldiazoalkane into the C-H bond of both aromatic and aliphatic aldehydes is described. In the presence of ch
Fe-catalyzed regiodivergent [1,2]-shift of α-aryl aldehydes
Gutierrez-Bonet, Alvaro,Flores-Gaspar, Areli,Martin, Ruben
supporting information, p. 12576 - 12579 (2013/09/23)
An Fe-catalyzed conversion of aldehydes to ketones via [1,2]-shift has been developed. This skeletal rearrangement shows a wide substrate scope and chemoselectivity profile while exhibiting an excellent [1,2]-aryl or [1,2]-alkyl shift selectivity that is easily switched by electronic effects.
A first homogeneous gold(III)-catalysed epoxidation of aromatic alkenes
Li, Xiao-Qiang,Li, Chen,Song, Fan-Bo,Zhang, Chi
, p. 722 - 724 (2008/09/20)
The first example of a homogeneous gold(III)-catalysed epoxidation of aromatic alkenes at room temperature using sodium chlorite as the stoichiometric oxidant in a homogeneous trisolvent system of 2-methoxyethanol/acetonitrile/ water (volume ratio: 1/3/1)
GaCl3-catalyzed skeletal rearrangement of α,α, α-trisubstituted aldehydes
Oshita, Masayuki,Okazaki, Takao,Ohe, Kouichi,Chatani, Naoto
, p. 331 - 334 (2007/10/03)
(Chemical Equation Presented) GaCl3 is found to be a superior catalyst for the skeletal rearrangement of α,α,α- trisubstituted aldehydes to ketones. The rearrangement can proceed smoothly in the presence of a catalytic amount of GaCl3, and even substrates having no heteroatoms α to the carbonyl group or without steric strains can be used. Double activation of a carbonyl group by two molecules of GaCl 3 was supported on the basis of experimental data and a DFT study.
α-hydrdroxylic acid derivatives, their production and use
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Page column 16, (2010/11/30)
The present invention relates to carboxylic acid derivatives of the formula where the radicals have the meanings stated in the description, to the preparation of these compounds and to their use as drugs.
Bismuth(III) oxide perchlorate promoted rearrangement of epoxides to aldehydes and ketones
Anderson, Andrew M.,Blazek, Jesse M.,Garg, Parie,Payne, Brian J.,Mohan, Ram S.
, p. 1527 - 1530 (2007/10/03)
Aryl-substituted epoxides and aliphatic epoxides with a tertiary epoxide carbon undergo smooth rearrangement in the presence of 10-50 mol% bismuth(III) oxide perchlorate, BiOClO4·XH2O, to give carbonyl compounds. The rearrangement is regioselective with aryl substituted epoxides and a single carbonyl compound arising from cleavage of benzylic C-O bond is formed. BiOClO4·XH2O is relatively non-toxic, insensitive to air and inexpensive, making this catalyst an attractive alternative to more corrosive and toxic Lewis acids such as BF3·Et2O or INCl3 currently used to effect epoxide rearrangements. (C) 2000 Elsevier Science Ltd.
Indium(III) chloride-promoted rearrangement of epoxides: A selective synthesis of substituted benzylic aldehydes and ketones
Ranu, Brindaban C.,Jana, Umasish
, p. 8212 - 8216 (2007/10/03)
A simple and efficient procedure for the rearrangement of substituted epoxides catalyzed by InCl3 has been developed. Aryl-substituted epoxides isomerize with complete regioselectivity to form a single carbonyl compound via cleavage of the benzylic C-O bond. The reactions are simple, fast, and high yielding. This procedure is very mild compared to those catalyzed with BF3 and other Lewis acids and compatible with several acid-sensitive functionalities. This protocol provides a highly selective synthesis of substituted benzylic aldehydes and ketones. However, rearrangement of alkyl- substituted epoxides is not very selective.