59786-32-2Relevant articles and documents
Nucleophilic aromatic substitution of methyl 3-nitropyridine-4-carboxylate
Holt, Jarle,Tjosa, Freddy,Bakke, Jan M.,Fiksdahl, Anne
, p. 987 - 989 (2004)
The nitro group of methyl 3-nitropyridine-4-carboxylate (1) has successfully been replaced by nitrogen, oxygen and sulphur nucleophiles by nucleophilic aromatic substitution to give the 3-azido, 3-methoxy, 3-phenoxy and 3-thiophenoxypyridine-4-carboxylate
Spin-Center Shift-Enabled Direct Enantioselective α-Benzylation of Aldehydes with Alcohols
Nacsa, Eric D.,MacMillan, David W. C.
supporting information, p. 3322 - 3330 (2018/03/13)
Nature routinely engages alcohols as leaving groups, as DNA biosynthesis relies on the removal of water from ribonucleoside diphosphates by a radical-mediated "spin-center shift" (SCS) mechanism. Alcohols, however, remain underused as alkylating agents in synthetic chemistry due to their low reactivity in two-electron pathways. We report herein an enantioselective α-benzylation of aldehydes using alcohols as alkylating agents based on the mechanistic principle of spin-center shift. This strategy harnesses the dual activation modes of photoredox and organocatalysis, engaging the alcohol by SCS and capturing the resulting benzylic radical with a catalytically generated enamine. Mechanistic studies provide evidence for SCS as a key elementary step, identify the origins of competing reactions, and enable improvements in chemoselectivity by rational photocatalyst design.
Synthetic Application of Lithiation Reactions: A Convenient Synthesis of 3,4-Dihydro-5-hydroxycarbostyril, 1,2,3,4-Tetrahydro-5-hydroxy-2-oxo-1,7-naphthyridine, and Methyl 3-Methoxypyridine-4-carboxylate
Tamura, Yasumitsu,Chen, Ling Ching,Fujita, Masanobu,Kita, Yasuyuki
, p. 1257 - 1262 (2007/10/02)
3,4-Dihydro-5-hydroxycarbostyril (3), a key intermediate for a clinically used β-receptor blocking agent (1), and its 7-aza analog (4) were prepared by an acid-catalyzed cyclization of the N-pivaloylamino-esters (17 and 19), which were obtained by using o