30708-63-5Relevant academic research and scientific papers
New chemistry of cyclic, s-trans-enaminones: Addition of Grignard reagents to enaminones derived from 2-methylcyclohexane-1,3-dione
Shawe, Thomas T.,Landino, Linda M.,Ross, Andrew A.,Prokopowicz, Anthony S.,Robinson, Patrice M.,Cannon, Annatina
, p. 3823 - 3824 (1996)
Grignard reagents add to cyclic s-trans enaminones to give the cycloalkenone after aqueous hydrolysis. In some cases a competitive double addition takes place. These reactions have been found to be solvent- and reagent-selective.
Palladium mediated one-pot synthesis of 3-aryl-cyclohexenones and 1,5-diketones from allyl alcohols and aryl ketones
Samser, Shaikh,Biswal, Priyabrata,Meher, Sushanta Kumar,Venkatasubbaiah, Krishnan
, p. 1386 - 1394 (2021/02/27)
One-pot synthesis of Robinson annulated 3-aryl-cyclohexenones from allyl alcohols and ketones using palladium is reported. Long chain aliphatic or aryl substitutions at the C1 position of allyl alcohol result in the formation of 1,5-diketone products. This simple one-pot method avoids the use of highly electrophilic vinyl ketones.
Synthesis of Ynolates via Double Deprotonation of Nonbrominated Esters
Sun, Jun,Yoshiiwa, Toshiya,Iwata, Takayuki,Shindo, Mitsuru
, p. 6585 - 6588 (2019/09/30)
Herein, we report a double deprotonation method used for the preparation of ynolates starting from nonbrominated 2,6-di-tert-butylphenyl esters. The current method is superior to the previously described double lithium/halogen exchange approach because easily accessible starting materials are used. This method will be especially useful for preparation of ynolates bearing functional groups in organic synthesis.
Synthesis of chiral seven-membered β-substituted lactams: Via Rh-catalyzed asymmetric hydrogenation
Huang, Yi,Li, Pan,Dong, Xiu-Qin,Zhang, Xumu
supporting information, p. 8819 - 8823 (2018/11/30)
Rh/bisphosphine-thiourea ligand (ZhaoPhos)-catalyzed asymmetric hydrogenation of seven-membered β-substituted α,β-unsaturated lactams was successfully developed to prepare various chiral seven-membered β-substituted lactams with good to excellent results (up to >99% conversion, 99% yield, and >99% ee).
Expedient Synthesis of 1,5-Diketones by Rhodium-Catalyzed Hydroacylation Enabled by C-C Bond Cleavage
Guo, Rui,Zhang, Guozhu
, p. 12891 - 12894 (2017/09/26)
A rhodium-catalyzed intermolecular hydroacylation reaction of vinyl cyclobutanols with non-chelating aldehydes has been developed. This reaction offers a new and atom-economical approach for the selective preparation of 1,5-diketones in high yields. Experimental data suggest a sequential ring-opening, transfer hydrogenation, and hydroacylation mechanism. We propose that aldehyde decarbonylation is avoided by the formation of a novel rhodium enolate species that also accounts for the compatibility of a broad range of aldehydes and its anti-Markovnikov selectivity.
Convenient Access to meta-Substituted Phenols by Palladium-Catalyzed Suzuki–Miyaura Cross-Coupling and Oxidation
Wang, Zi,Orellana, Arturo
supporting information, p. 11445 - 11449 (2017/08/26)
We report a new approach to the synthesis of meta-substituted phenols in which a single palladium catalyst accomplishes a Suzuki–Miyaura cross-coupling between a β-chlorocyclohexenone and an arylboronic acid, and oxidation of the resulting cyclohexenone to the corresponding phenol upon introduction of a terminal oxidant and electron transfer mediator. Notably, this method also allows ready access to ortho, meta-disubstituted phenols, sterically congested biaryl phenols, and more highly substituted phenols.
Synthesis of β-Substituted Cyclic Enones via Phosphonium Salt-Activated, Palladium-Catalyzed Cross-Coupling of Cyclic 1,3-Diones
Yang, Shyh-Ming,Kuo, Gee-Hong,Gaul, Michael D.,Murray, William V.
, p. 3464 - 3469 (2016/05/19)
Phosphonium salt-activated, Pd-catalyzed Suzuki-Miyaura and Sonogashira cross-coupling reactions of cyclic 1,3-diones in the synthesis of β-substituted cyclic enones are described. These transformations exhibit good isolated yield and high generality with respect to both substrates and coupling partners. Extension of the substrate scope to cyclic 1,3-dione equivalents, such as 2-cyanocyclohexanone (4), is also briefly examined.
Zn(II)- or Rh(I)-catalyzed rearrangement of silylated [1,1'-Bi(cyclopropan) ]-2'-en-1-ols
Zhang, Hang,Li, Changkun,Xie, Guojun,Wang, Bo,Zhang, Yan,Wang, Jianbo
, p. 6286 - 6293 (2014/07/21)
The rearrangement reactions of silylated alcohols bearing the highly strained structures of cyclopropene and cyclopropanol connected in adjacent positions have been studied under ZnI2- and Rh(I)-catalyzed conditions. The results show intriguing
Gold-catalyzed intramolecular carbocyclization of alkynyl ketones leading to highly substituted cyclic enones
Jin, Tienan,Yamamoto, Yoshinori
, p. 5259 - 5262 (2008/09/17)
(Chemical Equation Presented) The reaction of the internal alkynyl ketones 1 (n = 1) under the combined catalyst, AuCl3 and AgSbF6, gave the enones 2 in good to high yields, whereas that of the terminal alkynyl ketones 1 (n = 0) unde
Tandem nucleophilic addition/fragmentation reactions and synthetic versatility of vinylogous acyl triflates
Kamijo, Shin,Dudley, Gregory B.
, p. 6499 - 6507 (2007/10/03)
A thorough analysis of the chemistry of vinylogous acyl triflates provides insight into important chemical processes and opens new directions in synthetic technology. Tandem nucleophilic addition/C-C bond cleaving fragmentation reactions of cyclic vinylogous acyl triflates 1 yield a variety of acyclic acetylenic compounds. Full details are disclosed herein. A wide array of nucleophiles, such as organolithium and Grignard reagents, lithium enolates and their analogues, hydride reagents, and lithium amides, are applied. The respective reactions produce ketones 2, 1,3-diketones and their analogues 3, alcohols 4, and amides 5. The present reactions are proposed to proceed through a 1,2-addition of the nucleophile to the carbonyl group of starting triflates 1 to form tetrahedral alkoxide intermediates C, followed by Grob-type fragmentation, which effects C-C bond cleavage to yield acyclic acetylenic compounds 2-5 and 7. The potent nucleofugacity of the triflate moiety is channeled through the σ-bond framework of 1, providing direct access to the fragmentation pathway without denying other typical reactions of cyclic vinylogous esters. The synthetic versatility of vinylogous acyl triflates, including functionalization reactions of the cyclic enone core (1 → 6 or 8), is also illustrated.
