Nucleophile-Mediated Ring Expansion of 5-Acyl-substituted 4-Mesyloxymethyl-1,2,3,4-tetrahydropyrimidin-2-ones in the Synthesis of 7-Membered Analogues of Biginelli Compounds and Related Heterocycles

被引:13
|
作者
Fesenko, Anastasia A. [1 ]
Grigoriev, Mikhail S. [2 ]
Shutalev, Anatoly D. [1 ]
机构
[1] Moscow Technol Univ, Dept Organ Chem, 86 Vernadsky Ave, Moscow 119571, Russia
[2] Russian Acad Sci, AN Frumkin Inst Phys Chem & Electrochem, 31 Leninsky Ave, Moscow 119071, Russia
来源
JOURNAL OF ORGANIC CHEMISTRY | 2017年 / 82卷 / 15期
基金
俄罗斯基础研究基金会;
关键词
CALCIUM-CHANNEL BLOCKERS; CONTRACTION REACTIONS; DERIVATIVES; ELIMINATION;
D O I
10.1021/acs.joc.7b01348
中图分类号
O62 [有机化学];
学科分类号
070303 ; 081704 ;
摘要
A general six-step approach to alkyl 2-oxo-2,3,6,7-tetrahydro-1H-1,3-diazepine-5-carboxylates and 5-acy1-2,3,6,7-tetrahydto-1H-1,3-diazepin-2-ones based on the nucleophile-mediated ring expansion reaction of 5-functionalized 4-mesyloxymethyl-1,2,3,4-tetrahydropyrimidin-2-ones has been developed. Synthesis of the latter involved nucleophilic substitution of tosyl group in readily available N-(2-benzoyloxy-1-tosyl)ethyllurea with sodium enolates of,beta-oxoesters or 1,3-diketones, followed by dehydration or heterocyclization-dehydration of resulting products, removal of benzoyl protection,. and conversion of hydroxymethyl group into mesyloxymethyl group. Conformations of the obtained tetrahydro-1H-1,3-diazepin-2-ones in solid state and solutions were established using X-ray diffraction and NMR spectroscopy. A plausible mechanism of tetrahydropyrimidine ring expansion based on DFT calculation at B3LYP/6-31+G(d,p) level and NMR monitoring experiments was discussed. The ring contraction reaction of methoxy- or phenylthio-diazepinones under acidic conditions resulted in the corresponding 3-functionalized 1-carbamoy1-1H-pyrroles.
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页码:8085 / 8110
页数:26
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