73269-87-1Relevant academic research and scientific papers
Electrochemical deallylation of α-allyl cyclic amines and synthesis of optically active quaternary cyclic amino acids
Kirira, Peter G.,Kuriyama, Masami,Onomura, Osamu
experimental part, p. 3970 - 3982 (2010/07/04)
Electrochemical oxidation of α-allylated and α-betizylated N-acylated cyclic amines by using a graphite anode easily affords the corresponding α-methoxylated products with up to 76% yield. Ease of oxidation was affected by the type of electrode, the size
Ring contraction of of α,β-unsaturated cyclic amines with cis-dihydroxylation at the α,β-position
Libendi, Samuel S.,Demizu, Yosuke,Matsumura, Yoshihiro,Onomura, Osamu
experimental part, p. 311 - 321 (2009/09/06)
α,β-Unsaturated cyclic amines are oxidized by OsO4 to afford α,β-cis-dihydroxylated compounds which are thermodynamically transformed into ring-opened keto-alcohols. The keto-alcohols are then cyclized to form synthetically useful ring-contracted cyclic amines.
Exploratory synthetic studies of the α-methoxylation of amides via cuprous ion-promoted decomposition of o-diazobenzamides
Han, Gyoonhee,LaPorte, Matthew G.,McIntosh, Mathias C.,Weinreb, Steven M.,Parvez, Masood
, p. 9483 - 9493 (2007/10/03)
A convenient nonelectrochemical amide oxidation method has been developed. The process involves a cuprous ion-promoted decomposition of o-diazobenzamides like 4, generated in situ from the corresponding o-aminobenzamides, to give N-acyliminium ion intermediate 9 via a 1,5-H-atom transfer, followed by metal-catalyzed oxidation of the resulting α-amidyl radical. The transformation produces α-methoxybenzamides 15 in good yields. An attempt was made to apply this oxidation method to a total synthesis of the alkaloid (-)-anisomycin (16). Scalemic o-aminobenzamide pyrrolidine derivatives 18a/18b underwent oxidation to give α-methoxylated amide substrates 19a/19b, respectively, in good yields. However, alkylation of the N-acyliminium intermediate 20 with (p-methoxybenzyl)magnesium chloride gave the undesired anti-compounds 22a/22b as the major products. The amide oxidation exhibits good regioselectivity with many unsymmetrical 2-substituted piperidine and pyrrolidine systems. In general, it appears that the larger the C-2 substituent, the greater the methylene/methine H-atom abstraction ratio. A mechanistic rationale for this selectivity is suggested based upon amide rotamer populations. An extension of this methodology can be used to conduct two sequential amide oxidations using readily prepared 2-amino-6-nitrobenzamides such as 68 and 69.
A convenient synthetic method for amide oxidation
Han, Gyoonhee,McIntosh, Matthias C.,Weinreb, Steven M.
, p. 5813 - 5816 (2007/10/02)
Diazotization of o-aminobenzamides in methanol in the presence of a catalytic amount of CuCl affords α-methoxybenzamides in good yields.
