22020-87-7Relevant articles and documents
TRANSFORMATION OF 4-NITROALKANE-1,7-DIONES INTO PYRROLIZIDINES
Vavrecka, Mojmir,Janowitz, Agnes,Hesse, Manfred
, p. 5543 - 5546 (1991)
Depending on the conditions the reduction of 5-nitropentadecane-2,8-dione (4) gave as main products the two isomeric pyrrolizidines 1a (xenovenine, NaBH3CN/NH4OAc; as 15N-1a with NaBH3CN/15NH4OAc) and 1b (H2-Pd/C), respectively)
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Lewellyn,M.E.,Tarbell,D.S.
, p. 1407 - 1410 (1974)
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SYNTHESIS OF (+/-)-PYRENOPHORIN UTILIZING 1,3-DIPOLAR CYCLOADDITION OF SILYL NITRONATE FOR THE CONSTRUCTION OF 16-MEMBERED RING
Asaoka, Morio,Mukuta, Takashi,Takei, Hisashi
, p. 735 - 738 (1981)
1-Methyl-4-nitrobutyl acrylate underwent 1,3-dipolar cycloaddition via its silyl nitronate to give isoxazoline derivative of 16-membered dilactone after acid treatment, from which (+/-)-pyrenophorin was synthesized.
Basicities and Nucleophilicities of Pyrrolidines and Imidazolidinones Used as Organocatalysts
An, Feng,Maji, Biplab,Min, Elizabeth,Ofial, Armin R.,Mayr, Herbert
supporting information, p. 1526 - 1547 (2020/02/04)
The Br?nsted basicities pKaH (i.e., pKa of the conjugate acids) of 32 pyrrolidines and imidazolidinones, commonly used in organocatalytic reactions, have been determined photometrically in acetonitrile solution using CH acids as indicators. Most investigated pyrrolidines have basicities in the range 16 aH aH aH 12.6) and the 2-imidazoliummethyl-substituted pyrrolidine A21 (pKaH 11.1) are outside the typical range for pyrrolidines with basicities comparable to those of imidazolidinones. Kinetics of the reactions of these 32 organocatalysts with benzhydrylium ions (Ar2CH+) and structurally related quinone methides, common reference electrophiles for quantifying nucleophilic reactivities, have been measured photometrically. Most reactions followed second-order kinetics, first order in amine and first order in electrophile. More complex kinetics were observed for the reactions of imidazolidinones and several pyrrolidines carrying bulky 2-substituents, due to reversibility of the initial attack of the amines at the electrophiles followed by rate-determining deprotonation of the intermediate ammonium ions. In the presence of 2,4,6-collidine or 2,6-di-tert-butyl-4-methyl-pyridine, the deprotonation of the initial adducts became faster, which allowed the rate of the attack of the amines at the electrophiles to be determined. The resulting second-order rate constants k2 followed the correlation log?k2(20 °C) = sN(N + E), where electrophiles are characterized by one parameter (E) and nucleophiles are characterized by the two solvent-dependent parameters N and sN. In this way, the organocatalysts A1-A32 were integrated in our comprehensive nucleophilicity scale, which compares n-, -, and σ-nucleophiles. The nucleophilic reactivities of the title compounds correlate only poorly with their Br?nsted basicities.
A Modular and Diastereoselective 5 + 1 Cyclization Approach to N-(Hetero)Aryl Piperidines
Larsen, Matthew A.,Hennessy, Elisabeth T.,Deem, Madeleine C.,Lam, Yu-Hong,Saurí, Josep,Sather, Aaron C.
supporting information, p. 726 - 732 (2020/01/31)
A new general de novo synthesis of pharmaceutically important N-(hetero)aryl piperidines is reported. This protocol uses a robustly diastereoselective reductive amination/aza-Michael reaction sequence to achieve rapid construction of complex polysubstituted ring systems starting from widely available heterocyclic amine nucleophiles and carbonyl electrophiles. Notably, the diastereoselectivity of this process is enhanced by the presence of water, and DFT calculations support a stereochemical model involving a facially selective protonation of a water-coordinated enol intermediate.
ALDEHYDE-SELECTIVE WACKER-TYPE OXIDATION OF UNBIASED ALKENES
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Page/Page column 0140-0149; 0155-0164; 0166-0168; 0169, (2014/10/29)
This disclosure is directed to methods of preparing organic aldehydes, each method comprising contacting a terminal olefin with an oxidizing mixture comprising: (a) a dichloro-palladium complex; (b) a copper complex; (c) a source of nitrite; under aerobic reaction conditions sufficient to convert at least a portion of the terminal olefin to an aldehyde.