Synthesis of Imidazolidin-2-ones and Imidazol-2-ones via Base-Catalyzed Intramolecular Hydroamidation of Propargylic Ureas under Ambient Conditions

被引：21

作者：

Casnati, Alessandra ^{[1
]}

Perrone, Antonio ^{[1
]}

Mazzeo, Paolo P. ^{[1
,2
]}

Bacchi, Alessia ^{[1
,2
]}

Mancuso, Raffaella ^{[3
]}

Gabriele, Bartolo ^{[3
]}

Maggi, Raimondo ^{[1
]}

Maestri, Giovanni ^{[1
]}

Motti, Elena ^{[1
]}

Stirling, Andras ^{[4
]}

Della Ca', Nicola ^{[1
]}

机构：

[1] Univ Parma, Dept Chem Life Sci & Environm Sustainabil, I-43124 Parma, Italy

[2] Biopharmanet Tec, Parco Sci 27-A, I-43124 Parma, Italy

[3] Univ Calabria, Dipartimento Chim & Tecnol Chim, I-87036 Cosenza, Italy

[4] Res Ctr Nat Sci, Theoret Chem Res Grp, Inst Organ Chem, Budapest, Hungary

来源：

JOURNAL OF ORGANIC CHEMISTRY | 2019年 / 84卷 / 06期

关键词：

CYCLIC UREAS; OXIDATIVE CARBONYLATION; CESIUM HYDROXIDE; CARBON-DIOXIDE; MEDIATED HYDROAMINATION; ASYMMETRIC-SYNTHESIS; EFFICIENT SYNTHESIS; ALKYNES; AMINES; DIAMINES;

D O I：

10.1021/acs.joc.9b00064

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The first organo-catalyzed synthesis of imidazolidin-2-ones and imidazol-2-ones via intramolecular hydroamidation of propargylic ureas is reported. The phosphazene base BEMP turned out to be the most active organo-catalyst compared with guanidine and amidine bases. Excellent chemo- and regioselectivities to five-membered cyclic ureas have been achieved under ambient conditions, with a wide substrate scope and exceptionally short reaction times (down to 1 min). A base-mediated isomerization step to an allenamide intermediate is the most feasible reaction pathway to give imidazol-2-ones, as suggested by DFT studies.

引用

页码：3477 / 3490

页数：14

共 80 条

[41] Base-Mediated Direct Transformation of N-Propargylamines into 2,3,5-Trisubstituted 1H-Pyrroles [J].

Mishra, Pawan K. ;

Verma, Shalini ;

Kumar, Manoj ;

Verma, Akhilesh K. .

ORGANIC LETTERS, 2018, 20 (22) :7182-7185

[42]

Nakatsuji H., 2009, GAUSSIAN 09

[43] Gold(I)-Catalyzed Dearomative [2+21-Cycloaddition of Indoles with Activated Allenes: A Combined Experimental-Computational Study [J].

Ocello, Riccardo ;

De Nisi, Assunta ;

Jia, Minqiang ;

Yang, Qing-Qing ;

Monari, Magda ;

Giacinto, Pietro ;

Bottoni, Andrea ;

Miscione, Gian Pietro ;

Bandini, Marco .

CHEMISTRY-A EUROPEAN JOURNAL, 2015, 21 (50) :18445-18453

[44] Base-Mediated Hydroamination of Alkynes [J].

Patel, Monika ;

Saunthwal, Rakesh K. ;

Verma, Akhilesh K. .

ACCOUNTS OF CHEMICAL RESEARCH, 2017, 50 (02) :240-254

[45] Carbon Dioxide as a Carbonylating Agent in the Synthesis of 2-Oxazolidinones, 2-Oxazinones, and Cyclic Ureas: Scope and Limitations [J].

Paz, Jairo ;

Perez-Balado, Carlos ;

Iglesias, Beatriz ;

Munoz, Luis .

JOURNAL OF ORGANIC CHEMISTRY, 2010, 75 (09) :3037-3046

[46] Unexpected regio- and chemoselectivity of cationic gold-catalyzed cycloisomerizations of propargylureas: access to tetrasubstituted 3,4-dihydropyrimidin-2(1H)-ones [J].

Pereshivko, Olga P. ;

Peshkov, Vsevolod A. ;

Peshkov, Anatoly A. ;

Jacobs, Jeroen ;

Van Meervelt, Luc ;

Van der Eycken, Erik V. .

ORGANIC & BIOMOLECULAR CHEMISTRY, 2014, 12 (11) :1741-1750

[47] Cationic Gold- and Silver-Catalyzed Cycloisomerizations of Propargylic Ureas: A Selective Entry to Oxazolidin-2-imines and Imidazolidin-2-ones [J].

Pereshivko, Olga P. ;

Peshkov, Vsevolod A. ;

Jacobs, Jeroen ;

Van Meervelt, Luc ;

Van der Eycken, Erik V. .

ADVANCED SYNTHESIS & CATALYSIS, 2013, 355 (04) :781-789

[48] Tetrasubstituted 2-Imidazolones via Ag(I)-Catalyzed Cycloisomerization of Propargylic Ureas [J].

Peshkov, Vsevolod A. ;

Pereshivko, Olga P. ;

Sharma, Sweta ;

Meganathan, Thirumal ;

Parmar, Virinder S. ;

Ermolat'ev, Denis S. ;

Van der Eycken, Erik V. .

JOURNAL OF ORGANIC CHEMISTRY, 2011, 76 (14) :5867-5872

[49] Antineoplastic agents .362. Isolation and X-ray crystal structure of dibromophakellstatin from the Indian ocean sponge Phakellia mauritiana [J].

Pettit, GR ;

McNulty, J ;

Herald, DL ;

Doubek, DL ;

Chapuis, JC ;

Schmidt, JM ;

Tackett, LP ;

Boyd, MR .

JOURNAL OF NATURAL PRODUCTS, 1997, 60 (02) :180-183

[50] N-Amino-imidazolin-2-one Peptide Mimic Synthesis and Conformational Analysis [J].

Proulx, Caroline ;

Lubell, William D. .

ORGANIC LETTERS, 2012, 14 (17) :4552-4555

← 1 2 3 4 5 6 7 8 →