936-67-4Relevant articles and documents
Palladium-Catalyzed Alkene Carboalkoxylation Reactions of Phenols and Alcohols for the Synthesis of Carbocycles
White, Derick R.,Herman, Madeline I.,Wolfe, John P.
supporting information, p. 4311 - 4314 (2017/08/23)
Intermolecular alkene difunctionalization reactions between terminal alkenes bearing a pendant aryl or alkenyl triflate electrophile and exogenous alcohol or phenol nucleophiles are described. These transformations afford substituted indanyl or alkylidene
Direct palladium-catalyzed allylic alkylations of alcohols with enamines: Synthesis of homoallyl ketones
Bouhalleb, Ghalia,Mhasni, Olfa,Poli, Giovanni,Rezgui, Farhat
supporting information, p. 2525 - 2529 (2017/06/13)
An efficient, direct nucleophilic allylic substitution of α-, β- and γ-substituted alcohols with enamines, using the Pd(OAc)2/PPh3 catalyst system and ZnBr2 as a promoter in CH2Cl2 at reflux, is reported. The reaction course was dependent on the steric hindrance at the α- or γ-positions with respect to the functionalized α-carbon, selectively affording in moderate to good yields, α- or γ-homoallyl ketones, the so-called “linear” and “branched” products, respectively.
Hydrogen-bond-activated palladium-catalyzed allylic alkylation via allylic alkyl ethers: Challenging leaving groups
Huo, Xiaohong,Quan, Mao,Yang, Guoqiang,Zhao, Xiaohu,Liu, Delong,Liu, Yangang,Zhang, Wanbin
supporting information, p. 1570 - 1573 (2014/04/17)
C-O bond cleavage of allylic alkyl ether was realized in a Pd-catalyzed hydrogen-bond-activated allylic alkylation using only alcohol solvents. This procedure does not require any additives and proceeds with high regioselectivity. The applicability of this transformation to a variety of functionalized allylic ether substrates was also investigated. Furthermore, this methodology can be easily extended to the asymmetric synthesis of enantiopure products (99% ee).
Dual palladium-and proline-catalyzed allylic alkylation of enolizable ketones and aldehydes with allylic alcohols
Usui, Ippei,Schmidt, Stefan,Breit, Bernhard
supporting information; experimental part, p. 1453 - 1456 (2009/09/30)
The dual Pd/proline-catalyzed α-allylation reaction of a variety of enolizable ketones and aldehydes with allylic alcohols is described. In this reaction, the choice of a large-bite angle ligand Xantphos and proline as the organocatalyst was essential for generation of the crucial π-allyl Pd intermediate from allylic alcohol, followed by nucleophilic attack of the enamine formed in situ from the corresponding enolizable carbonyl substrate and proline.
Halonium ion-mediated reaction of unsaturated hydroperoxy acetals. Competition between the formation of cyclic peroxides and the migration of the methoxy (or hydroxy) group
Tokuyasu, Takahiro,Masuyama, Araki,Nojima, Masatomo,McCullough, Kevin J.
, p. 1069 - 1075 (2007/10/03)
Monoozonolyses of dienes 2 in methanol gave in each case the corresponding unsaturated α-methoxy hydroperoxides 3. Capture of 2-alkyl- substituted cyclohexanone oxides by methanol was highly diastereoselective, thereby providing exclusively the hydroperoxides derived from attack by methanol from the less hindered face of the carbonyl oxide intermediates. Halonium ion-mediated reactions of the hydroperoxides 3 gave the novel methoxy- or hydroxy-migrated products, together with the expected halogen- substituted 1,2-dioxanes and/or 1,2-dioxepanes, the composition of the product mixture being a function of the halogenating agent utilized and the structure of 3.
A synthetic approach to perhydro-3-isoquinolinones bearing an angular methyl group via organocuprate addition
Stanetty, Peter,Bahardoust, M. Hassan,Mihovilovic, Marko D.,Mereiter, Kurt
, p. 1257 - 1268 (2007/10/03)
The addition of organocuprates to the activated C-C double bond in 2H-3,3a,4,5,6,7-hexahydro-2-indenone followed by trapping of the anionic intermediate with Mel as electrophile is reported. Structural assignment of the resulting product was carried out v
Regioselective α-alkylation of silyl enolates using a mild catalyst- ZnCl2 doped on acidic alumina
Kad,Singh, Vasundhara,Khurana, Anupam,Chaudhary, Sangeeta,Singh, Jasvinder
, p. 3439 - 3442 (2007/10/03)
ZnCl2 doped acidic alumina used as a solid support acts as a better Lewis acid in the S(N)1 reaction of trimethyl silyl enol ethers with 30, allylic and benzylic halides to yield exclusively the substituted product in excellent yields. This method has been employed for the synthesis of monocyclic sesquitepene hydrocarbon, (+)-β-bisabolene and a monoterpene, 2,6-dimethyl-7-octen-4-one.
Organoaluminum-Promoted Cyclization of Olefinic Epoxides. a New and Stereoselective Approach to Cyclohexane Frameworks
Murase, Noriaki,Maruoka, Keiji,Ooi, Takashi,Yamamoto, Hisashi
, p. 707 - 711 (2007/10/03)
A new, general synthetic method of six-membered carbocycles has been demonstrated, which involves the stereo-controlled cyclization of olefinic epoxides with methylaluminum bis(4-bromo-2,6-di-t-butylphenoxide) (MABR) via the epoxide rearrangement and subsequent intramolecular ene reaction with high stereoselectivity. This strategy is shown to be highly useful in the stereoselective synthesis of the basic skeleton of various terpenes.
Versatile Desilylative Cross-Coupling of Silyl Enol Ethers and Allylic Silanes via Oxovanadium-Induced Chemoselective One-Electron Oxidation
Hirao, Toshikazu,Fujii, Takashi,Ohshiro, Yoshiki
, p. 10207 - 10214 (2007/10/02)
The chemoselective cross-coupling of silyl enol ethers and allylic silanes to γ,δ-unsaturated ketones is achieved by the oxovanadium(V)-induced oxidative desilylation of the more readily oxidizable organosilicon compounds.
Convenient Radical α-Monoallylations of Carbonyl Compounds
Watanabe, Yoshihiko,Yoneda, Tetsuo,Okumura, Tatsuya,Ueno, Yoshio,Toru, Takeshi
, p. 3030 - 3033 (2007/10/02)
Free radical allylations of α-seleno carbonyl compounds with tributyl-substituted 2,4-pentadienyltin, 2-methyl-2-propenyltin, 2-butenyltin, and 3-methyl-2-butenyltin, are described. Such successful C-C bond formations, in particular with the 2-butenyltin and the 3-methyl-2-butenyltin, are owing to the high reactivity of the α-carbon radical, generated from α-seleno carbonyl compounds, toward allylic tin compounds.
