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61.
62.
The rate of cyclization of pentafluoro- (1) and 4-Cl-2,3,5,6-tetrafluoro-2-NHY-diphenyl ethers (2a, Y=Ac;2b, Y=H;2c, Y=Me) to form phenoxazines on refluxing in DMF increases with an increase in the nucleophilicity of the amino group. The cyclization of the N-acetyl derivative2a is followed by the Smiles rearrangement, whereas the transformation of ethers2b andc, containing free amino and N-methylamino groups, respectively, includes mainly an attack on the amino group at theortho-position of the fluorinated ring. In the case of ether2c, introduction of K2CO3 into the reaction mixture results in cyclization with the Smiles rearrangement.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1101–1105, June, 1993. 相似文献
63.
Martin Chwalek 《Tetrahedron letters》2004,45(24):4749-4753
The isomaltose trichloroacetimidate 7 was synthesized in five steps from d-amygdalin. The key step in this series of reactions was the acid catalyzed rearrangement of the inter-glycosydic bond to give the thermodynamically more stable α-anomer. The reaction was also applied to different di-, tri-, and tetrasaccharide derivatives of amygdalin giving the corresponding rearrangement products. 相似文献
64.
65.
The aziridinium ylide generated by the intramolecular reaction of a metal carbenoid tethered to a vinylaziridine undergoes [2,3]-Stevens rearrangement to furnish the indolizidine skeleton. It is essential that the correct nitrogen invertomer is used or a competing [1,5]-hydrogen shift predominates. During the preparation of a second system a `one-pot' acylation-[3,3]-Claisen rearrangement was observed, delivering a seven-membered lactam. 相似文献
66.
Ana Montero 《Tetrahedron letters》2005,46(3):401-405
A stereocontrolled synthesis of an unsaturated sugar bearing two amino groups (one of them masked as an azide), using an Overman rearrangement as key step, is described. This scaffold is used to prepare two peptides having aromatic fragments, which have shown activity as calpain inhibitors. 相似文献
67.
68.
Akira Ando 《Journal of fluorine chemistry》2005,126(5):765-770
Treatment of 2-chloro-3,3-difluoroprop-2-en-1-ol derivatives (2) with methanesulfonyl chloride in the presence of a base did not give the expected esters but 2-chloro-1,1-difluoroprop-2-enyl methanesulfonates (4) through a novel [3,3] sigmatropic rearrangement. Reaction of 4 with diethylzinc in the presence of tetrakis(triphenylphosphine) palladium gave 1-alkyl- or 1-aryl-2-chloro-3-fluoropenta-1,3-dienes in moderate to good yields through a CC bond formation followed by dehydrofluorination. 相似文献
69.
Halland N Alstrup Lie M Kjaersgaard A Marigo M Schiøtt B Jørgensen KA 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(23):7083-7090
The mechanism for the 2,5-diphenylpyrrolidine-catalyzed enantioselective alpha-chlorination of aldehydes with electrophilic halogenation reagents has been investigated by using experimental and computational methods. These studies have led us to propose a mechanism for the reaction that proceeds through an initial N-chlorination of the chiral catalyst-substrate complex, followed by a 1,3-sigmatropic shift of the chlorine atom to the enamine carbon atom. The suggested reaction course is different from previously proposed mechanisms for organocatalytic enamine reactions, in which the carbon-electrophile bond is formed directly. Furthermore, the rate-determining step in the overall reaction was determined and the presence of nonlinear effects was probed. 相似文献
70.