Enantioselective Desymmetrization of 1,4-Dihydropyridines by Oxidative NHC Catalysis

被引：15

作者：

Di Carmine, Graziano ^{[1
]}

Ragno, Daniele ^{[1
]}

Brandolese, Arianna ^{[1
]}

Bortolini, Olga ^{[1
]}

Pecorari, Daniel ^{[2
]}

Sabuzi, Federica ^{[3
]}

Mazzanti, Andrea ^{[2
]}

Massi, Alessandro ^{[1
]}

机构：

[1] Univ Ferrara, Dept Chem & Pharmaceut Sci, Via L Borsari 46, I-44121 Ferrara, Italy

[2] Univ Bologna, Dept Ind Chem Toso Montanari, V Risorgimento 4, I-40136 Bologna, Italy

[3] Univ Roma Tor Vergata, Dept Chem Sci & Technol, V Ric Sci, I-00131 Rome, Italy

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2019年 / 25卷 / 31期

关键词：

carbenes; desymmetrization; density functional calculations; dihydropyridines; organocatalysis; NUCLEOPHILIC DEAROMATIZATION; ASYMMETRIC-SYNTHESIS; ENANTIOMERS; PYRIDINES; ACCESS; DISCOVERY; REDUCTION; ALDEHYDES; INDOLES; DESIGN;

D O I：

10.1002/chem.201901243

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The unprecedented desymmetrization of prochiral dialdehydes catalyzed by N-heterocyclic carbenes under oxidative conditions was applied to the highly enantioselective synthesis of 1,4-dihydropyridines (DHPs) starting from 3,5-dicarbaldehyde substrates. Synthetic elaboration of the resulting 5-formyl-1,4-DHP-3-carboxylates allowed for access to the class of pharmaceutically relevant 1,4-DHP-3,5-dicarboxylates (Hantzsch esters). DFT calculations suggested that the enantioselectivity of the process is determined by the transition state involving the oxidation of the Breslow intermediate by the external quinone oxidant.

引用

页码：7469 / 7474

页数：6

共 50 条

[21] Vicinal diamination of 1,4-dihydropyridines
Lavilla, R
Kumar, R
Coll, O
Masdeu, C
Bosch, J
CHEMICAL COMMUNICATIONS, 1998, (24) : 2715 - 2716
[22] Progress in Synthesis of 1,4-Dihydropyridines
Lu, Lingling
Xu, Hui
Zhou, Pan
Yu, Fuchao
CHINESE JOURNAL OF ORGANIC CHEMISTRY, 2016, 36 (12) : 2858 - 2879
[23] NOVEL FLUORESCENT 1,4-DIHYDROPYRIDINES
NAIR, V
OFFERMAN, RJ
TURNER, GA
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 1986, 192 : 271 - ORGN
[24] Novel Oxidation of 1,4-Dihydropyridines
Hatamjafari, Farhad
Montazeri, Nasser
Pourshamsian, Khalil
ASIAN JOURNAL OF CHEMISTRY, 2011, 23 (07) : 3287 - 3288
[25] Effect of rosemary and 1,4-dihydropyridines on oxidative and flavour changes of bergamot oil
Pudil, F
Volfova, J
Janda, V
Valentova, H
Pokorny, J
FOOD FLAVORS: FORMATION, ANALYSIS, AND PACKAGING INFLUENCES, 1998, 40 : 679 - 687
[26] PROTEASE-CATALYZED ENANTIOSELECTIVE SYNTHESIS OF OPTICALLY-ACTIVE 1,4-DIHYDROPYRIDINES
HIROSE, Y
KARIYA, K
SASAKI, I
KURONO, Y
ACHIWA, K
TETRAHEDRON LETTERS, 1993, 34 (21) : 3441 - 3444
[27] Graphite oxide mediated oxidative aromatization of 1,4-dihydropyridines into pyridine derivatives
Mirza-Aghayan, Maryam
Boukherroub, Rabah
Nemati, Mohammad
Rahimifard, Mahshid
TETRAHEDRON LETTERS, 2012, 53 (19) : 2473 - 2475
[28] Oxidative aromatization of some 1,4-dihydropyridines by aqueous hydrogen peroxide in ethanol
Abdoli-Senejani, Masumeh
Hajibabaei, Maryam
IRANIAN CHEMICAL COMMUNICATION, 2015, 3 (02) : 174 - 179
[29] Aromatization of Hantzsch 1,4-dihydropyridines with Magtrieve™
Ko, KY
Kim, JY
TETRAHEDRON LETTERS, 1999, 40 (16) : 3207 - 3208
[30] RECYCLIZATION OF 1,4-DIHYDROPYRIDINES IN ACIDIC MEDIA
LUSIS, VK
MUTSENIETSE, DK
DUBUR, GY
KHIMIYA GETEROTSIKLICHESKIKH SOEDINENII, 1987, (09): : 1285 - 1286

← 1 2 3 4 5 →