17429-36-6Relevant academic research and scientific papers
Synthetic and Mechanistic Studies on the Rhodium-Catalyzed Redox Isomerization of Cyclohexa-2,5-dienols
Kress, Steffen,Johnson, Thomas,Weisshar, Florian,Lautens, Mark
, p. 747 - 750 (2016)
We report the application of cyclohexa-2,5-dienols in a catalytic redox isomerization: a rhodium-catalyzed desymmetrization for the synthesis of Υ,Υ-disubstituted cyclohexenones. The reaction generates products which are useful intermediates in organic sy
Rhodium-Catalyzed Desymmetric Arylation of γ,γ-Disubsituted Cyclohexadienones: Asymmetric Synthesis of Chiral All-Carbon Quaternary Centers
Qiao, Yu,Bai, Shiming,Wu, Xiao-Feng,Yang, Ying,Meng, He,Ming, Jialin
, p. 1556 - 1560 (2022/02/23)
The desymmetric arylation of prochiral cyclohexadienones with ArZnCl in the presence of an (R)-segphos-rhodium catalyst gave high yields of the corresponding cyclohexenones, which contain a chiral arylated carbon center at the β-position and a chiral all-carbon quaternary center at the γ-position, with high diastereo- and enantioselectivities. This catalytic system was also applied to the arylation of spirocarbocyclic cyclohexadienones and afforded the corresponding cyclohexenones bearing a chiral spiro quaternary carbon with high dr and ee.
The Silicon-Hydrogen Exchange Reaction: A Catalytic σ-Bond Metathesis Approach to the Enantioselective Synthesis of Enol Silanes
Zhou, Hui,Bae, Han Yong,Leutzsch, Markus,Kennemur, Jennifer L.,Bécart, Diane,List, Benjamin
supporting information, p. 13695 - 13700 (2020/08/24)
The use of chiral enol silanes in fundamental transformations such as Mukaiyama aldol, Michael, and Mannich reactions as well as Saegusa-Ito dehydrogenations has enabled the chemical synthesis of enantiopure natural products and valuable pharmaceuticals. However, accessing these intermediates in high enantiopurity has generally required the use of either stoichiometric chiral precursors or stoichiometric chiral reagents. We now describe a catalytic approach in which strongly acidic and confined imidodiphosphorimidates (IDPi) catalyze highly enantioselective interconversions of ketones and enol silanes. These "silicon-hydrogen exchange reactions"enable access to enantiopure enol silanes via tautomerizing σ-bond metatheses, either in a deprotosilylative desymmetrization of ketones with allyl silanes as the silicon source or in a protodesilylative kinetic resolution of racemic enol silanes with a carboxylic acid as the silyl acceptor.
Strong and Confined Acids Control Five Stereogenic Centers in Catalytic Asymmetric Diels–Alder Reactions of Cyclohexadienones with Cyclopentadiene
Bistoni, Giovanni,Das, Sayantani,De, Chandra Kanta,Ghosh, Santanu,Leutzsch, Markus,List, Benjamin,Neese, Frank,Yepes, Diana
supporting information, p. 12347 - 12351 (2020/03/23)
We describe a highly enantioselective Diels–Alder reaction of cross-conjugated cyclohexadienones with cyclopentadiene, in which five stereocenters are effectively controlled by a strongly acidic and confined imidodiphosphorimidate catalyst. Our approach provides tricyclic products in excellent stereoselectivity. We also report methods to convert the obtained products into useful intermediates and a computational study that aids in gaining deeper insight into the reaction mechanism and origin of stereoselectivity.
Nickel-Catalyzed Desymmetric Hydrogenation of Cyclohexadienones: An Efficient Approach to All-Carbon Quaternary Stereocenters
You, Cai,Li, Xiuxiu,Gong, Quan,Wen, Jialin,Zhang, Xumu
supporting information, p. 14560 - 14564 (2019/10/11)
Nickel-catalyzed desymmetric hydrogenation has been achieved. With the Ni(OTf)2/(S,S)-Ph-BPE system, a series of ?,?-disubstituted cyclohexadienones were transformed to the corresponding cyclohexenones with a chiral all-carbon quaternary center at the γposition in high yields (92-98%) and excellent enantioselectivities (92%-99% ee). This catalytic system can also tolerate the desymmetric reaction of spirocarbocyclic cyclohexadienones to produce the corresponding cyclohexenones bearing a chiral spiro quaternary carbon with high yields (94%-98%) and ee values (96%-99% ee). Furthermore, this methodology provides an efficient and concise synthetic route to the intermediate of natural products cannabispirenones A and B.
Asymmetric Synthesis of Remote Quaternary Centers by Copper-Catalyzed Desymmetrization: An Enantioselective Total Synthesis of (+)-Mesembrine
Bokka, Apparao,Mao, James X.,Hartung, John,Martinez, Steven R.,Simanis, Justin A.,Nam, Kwangho,Jeon, Junha,Shen, Xiaoqiang
supporting information, p. 5158 - 5162 (2018/09/13)
Catalytic asymmetric syntheses of remote quaternary stereocenters have been developed by copper-catalyzed 1,4-hydrosilylation of ?,?-disubstituted cyclohexadienones. A variety of cyclohexenones have been synthesized in good yield and excellent enantioselectivity. Versatile 2-silyloxy diene intermediates bearing ?,?-disubstituted all carbon stereogenic centers can be isolated from the mild reaction conditions. The utility of this strategy is exemplified in a catalytic asymmetric total synthesis of (+)-mesembrine.
Palladium-Catalyzed α-Arylation of Vinylogous Esters for the Synthesis of γ,γ-Disubstituted Cyclohexenones
Johnson, Thomas,Pultar, Felix,Menke, Friedericke,Lautens, Mark
, p. 6488 - 6491 (2016/12/23)
A palladium-catalyzed α-arylation of cyclic vinylogous esters to form products that are converted in one step to γ-alkyl-γ-aryl-substituted cyclohexenones is reported. This Pd-catalyzed reaction proceeds at room temperature, is generally high-yielding, and uses an amount of a commercially available catalyst as low as 0.25 mol %. The scope of aryl bromides is particularly broad, and alkenyl bromides can also be used. This two-step protocol, comprising α-arylation and reductive transposition, can be performed in one pot and is applicable to gram-scale synthesis.
Asymmetric Induction at Remote Quaternary Centers of Cyclohexadienones by Rhodium-Catalyzed Conjugate Hydrosilylation
Naganawa, Yuki,Kawagishi, Mayu,Ito, Jun-Ichi,Nishiyama, Hisao
, p. 6873 - 6876 (2016/06/13)
The enantioselective desymmetrizing conjugate hydrosilylation of prochiral differently γ,γ-disubstituted cyclohexadienone derivatives 2 to furnish the corresponding cyclohexenones 4 with a remote chiral all-carbon quaternary center at the γ position is de
Palladium-catalyzed γ-arylation of β,γ-unsaturated ketones: Application to a one-pot synthesis of tricyclic indolines
Hyde, Alan M.,Buchwald, Stephen L.
, p. 177 - 180 (2008/09/18)
(Chemical Equation Presented) Indolines in short order: A catalyst system which allows for efficient γ-arylation of β,γ-unsaturated ketones is described (see scheme; dippf = 1,1′-bis(diisopropylphosphanyl) ferrocene, dba = trans,transdibenzylideneacetone). This method can be applied to a one-pot, two-step synthesis of polycyclic indolines from simple starting materials.
Indazole or indole derivatives, and use thereof in human medicine and more particularly in oncology
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Page 24, (2010/02/08)
The present invention relates to novel compounds derived from indazoles or indoles of formula (1) or formula (2), to methods for treating tumors or cancerous cells with compounds of formula (1) or formula (2) and to pharmacaetutical compositions comprisin
