Synthesis of N-H Bearing Imidazolidinones and Dihydroimidazolones Using Aza-Heck Cyclizations

Overview

Journal Angew Chem Int Ed Engl

Specialty Chemistry

Date 2018 Aug 21

PMID 30125443

Citations 9

Authors

Feiyang Xu

Scott A Shuler

Donald A Watson

Affiliations

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Abstract

The synthesis of unsaturated, unprotected imidazolidinones via an aza-Heck reaction is described. This palladium-catalyzed process allows for the cyclization of N-phenoxy ureas onto pendant alkenes. The reaction has broad functional group tolerance, can be applied to complex ring topologies, and can be used to directly prepare mono- and bis-unprotected imidazolidinones. By addition of Bu NI, dihydroimidazolones can be accessed from the same starting materials. Improved conditions for preparing unsaturated, unprotected lactams are also reported.

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References

Kwak S, Bang S, Seo H, Shin H, Lee K, Le Hoang T . Evaluation of anticancer activity of 4-vinyl-1-arylsulfonylimidazolidinones. Arch Pharm Res. 2006; 29(9):721-7. DOI: 10.1007/BF02974070. View

Xiong P, Xu F, Qian X, Yohannes Y, Song J, Lu X . Copper-Catalyzed Intramolecular Oxidative Amination of Unactivated Internal Alkenes. Chemistry. 2016; 22(13):4379-83. DOI: 10.1002/chem.201600329. View

Wu M, Fan T, Chen S, Han Z, Gong L . Pd(II)-Catalyzed Asymmetric Oxidative 1,2-Diamination of Conjugated Dienes with Ureas. Org Lett. 2018; 20(8):2485-2489. DOI: 10.1021/acs.orglett.8b00870. View

Rao W, Yin X, Shi B . Catalyst-Controlled Amino- versus Oxy-Acetoxylation of Urea-Tethered Alkenes: Efficient Synthesis of Cyclic Ureas and Isoureas. Org Lett. 2015; 17(15):3758-61. DOI: 10.1021/acs.orglett.5b01741. View

Zhu Y, Cornwall R, Du H, Zhao B, Shi Y . Catalytic diamination of olefins via N-N bond activation. Acc Chem Res. 2014; 47(12):3665-78. PMC: 4270412. DOI: 10.1021/ar500344t. View

Bronson J, DenBleyker K, Falk P, Mate R, Ho H, Pucci M . Discovery of the first antibacterial small molecule inhibitors of MurB. Bioorg Med Chem Lett. 2003; 13(5):873-5. DOI: 10.1016/s0960-894x(02)01076-4. View

Kazmierski W, Furfine E, Gray-Nunez Y, Spaltenstein A, Wright L . Potent inhibitors of the HIV-1 protease incorporating cyclic urea P1-P2 scaffold. Bioorg Med Chem Lett. 2004; 14(22):5685-7. DOI: 10.1016/j.bmcl.2004.08.038. View

Wolfe J . Palladium-Catalyzed Carboetherification and Carboamination Reactions of γ-Hydroxy- and γ-Aminoalkenes for the Synthesis of Tetrahydrofurans and Pyrrolidines. European J Org Chem. 2010; 2007(4):571-582. PMC: 2890284. View

Kim M, Mulcahy J, Espino C, Du Bois J . Expanding the substrate scope for C-H amination reactions: oxidative cyclization of urea and guanidine derivatives. Org Lett. 2006; 8(6):1073-6. DOI: 10.1021/ol052920y. View

10.

Race N, Hazelden I, Faulkner A, Bower J . Recent developments in the use of aza-Heck cyclizations for the synthesis of chiral N-heterocycles. Chem Sci. 2017; 8(8):5248-5260. PMC: 5606024. DOI: 10.1039/c7sc01480e. View

11.

Robinson D, Curran M, Lyseng-Williamson K . Imidapril: a review of its use in essential hypertension, Type 1 diabetic nephropathy and chronic heart failure. Drugs. 2007; 67(9):1359-78. DOI: 10.2165/00003495-200767090-00008. View

12.

Jia J, Ho Y, Bulow R, Rueping M . Brønsted Base Assisted Photoredox Catalysis: Proton Coupled Electron Transfer for Remote C-C Bond Formation via Amidyl Radicals. Chemistry. 2018; 24(53):14054-14058. DOI: 10.1002/chem.201802907. View

13.

Race N, Faulkner A, Shaw M, Bower J . Dichotomous mechanistic behavior in Narasaka-Heck cyclizations: electron rich Pd-catalysts generate iminyl radicals. Chem Sci. 2018; 7(2):1508-1513. PMC: 5963672. DOI: 10.1039/c5sc04037j. View

14.

Zaman S, Mitsuru K, Abell A . Synthesis of trisubstituted imidazoles by palladium-catalyzed cyclization of O-pentafluorobenzoylamidoximes: application to amino acid mimetics with a C-terminal imidazole. Org Lett. 2005; 7(4):609-11. DOI: 10.1021/ol047628p. View

15.

Shen K, Wang Q . Copper-catalyzed aminoalkynylation of alkenes with hypervalent iodine reagents. Chem Sci. 2018; 8(12):8265-8270. PMC: 5857935. DOI: 10.1039/c7sc03420b. View

16.

Faulkner A, Scott J, Bower J . An Umpolung Approach to Alkene Carboamination: Palladium Catalyzed 1,2-Amino-Acylation, -Carboxylation, -Arylation, -Vinylation, and -Alkynylation. J Am Chem Soc. 2015; 137(22):7224-30. DOI: 10.1021/jacs.5b03732. View

17.

Pirard B, Matter H . Matrix metalloproteinase target family landscape: a chemometrical approach to ligand selectivity based on protein binding site analysis. J Med Chem. 2006; 49(1):51-69. DOI: 10.1021/jm050363f. View

18.

Shen K, Wang Q . Copper-catalyzed diamination of unactivated alkenes with hydroxylamines. Chem Sci. 2017; 6(7):4279-4283. PMC: 5707484. DOI: 10.1039/c5sc00897b. View

19.

Kitamura M, Narasaka K . Synthesis of aza-heterocycles from oximes by amino-Heck reaction. Chem Rec. 2002; 2(4):268-77. DOI: 10.1002/tcr.10030. View

20.

Ma Y, De S, Chen C . Syntheses of Cyclic Guanidine-Containing Natural Products. Tetrahedron. 2015; 71(8):1145-1173. PMC: 4325426. DOI: 10.1016/j.tet.2014.11.056. View