Synthesis of Enantiomerically Enriched Imidazolidin‐2‐Ones through Asymmetric Palladium‐Catalyzed Alkene Carboamination Reactions
dc.contributor.author | Hopkins, Brett A. | en_US |
dc.contributor.author | Wolfe, John P. | en_US |
dc.date.accessioned | 2012-10-02T17:19:58Z | |
dc.date.available | 2013-10-18T17:47:30Z | en_US |
dc.date.issued | 2012-09-24 | en_US |
dc.identifier.citation | Hopkins, Brett A.; Wolfe, John P. (2012). "Synthesis of Enantiomerically Enriched Imidazolidin‐2‐Ones through Asymmetric Palladium‐Catalyzed Alkene Carboamination Reactions ." Angewandte Chemie International Edition 51(39): 9886-9890. <http://hdl.handle.net/2027.42/93659> | en_US |
dc.identifier.issn | 1433-7851 | en_US |
dc.identifier.issn | 1521-3773 | en_US |
dc.identifier.uri | https://hdl.handle.net/2027.42/93659 | |
dc.publisher | WILEY‐VCH Verlag | en_US |
dc.subject.other | Stereoselectivity | en_US |
dc.subject.other | Palladium | en_US |
dc.subject.other | Heterocycles | en_US |
dc.subject.other | Asymmetric Catalysis | en_US |
dc.subject.other | Asymmetric Synthesis | en_US |
dc.title | Synthesis of Enantiomerically Enriched Imidazolidin‐2‐Ones through Asymmetric Palladium‐Catalyzed Alkene Carboamination Reactions | en_US |
dc.type | Article | en_US |
dc.rights.robots | IndexNoFollow | en_US |
dc.subject.hlbsecondlevel | Chemistry | en_US |
dc.subject.hlbtoplevel | Science | en_US |
dc.description.peerreviewed | Peer Reviewed | en_US |
dc.contributor.affiliationum | Department of Chemistry, University of Michigan, 930 N. University Ave, Ann Arbor, MI 48109‐1055 (USA) | en_US |
dc.contributor.affiliationum | Department of Chemistry, University of Michigan, 930 N. University Ave, Ann Arbor, MI 48109‐1055 (USA) | en_US |
dc.identifier.pmid | 22936415 | en_US |
dc.description.bitstreamurl | http://deepblue.lib.umich.edu/bitstream/2027.42/93659/1/9886_ftp.pdf | |
dc.description.bitstreamurl | http://deepblue.lib.umich.edu/bitstream/2027.42/93659/2/anie_201205233_sm_miscellaneous_information.pdf | |
dc.identifier.doi | 10.1002/anie.201205233 | en_US |
dc.identifier.source | Angewandte Chemie International Edition | en_US |
dc.identifier.citedreference | P. B. White, S. S. Stahl, J. Am. Chem. Soc. 2011, 133, 18594 – 18597. | en_US |
dc.identifier.citedreference | S. Rousseaux, J. Garcia‐Fortanet, M. A. Del Aguila Sanchez, S. L. Buchwald, J. Am. Chem. Soc. 2011, 133, 9282 – 9285. | en_US |
dc.identifier.citedreference | In contrast to asymmetric reactions of N ‐allyl ureas, transformations of N ‐Boc‐pent‐4‐enylamine derivatives proceed with similar enantioselectivities for both aryl iodide and aryl bromide substrates. See Ref. [7a]. | en_US |
dc.identifier.citedreference | For studies on the mechanism of syn ‐migratory insertion of alkenes into PdN bonds, see: | en_US |
dc.identifier.citedreference | J. D. Neukom, N. S. Perch, J. P. Wolfe, J. Am. Chem. Soc. 2010, 132, 6276 – 6277; | en_US |
dc.identifier.citedreference | P. S. Hanley, D. Markovic, J. F. Hartwig, J. Am. Chem. Soc. 2010, 132, 6302 – 6303; | en_US |
dc.identifier.citedreference | J. D. Neukom, N. S. Perch, J. P. Wolfe, Organometallics 2011, 30, 1269 – 1277; | en_US |
dc.identifier.citedreference | P. S. Hanley, J. F. Hartwig, J. Am. Chem. Soc. 2011, 133, 15661 – 15673; | en_US |
dc.identifier.citedreference | Our estimation of the relative electron‐richness of the N ‐Boc pentenylamine versus the p ‐nitrophenyl urea are based on a comparison of p K a values for N 1, N 1 ‐dimethyl‐ N 2 ‐( p ‐nitrophenyl)urea (p K a =15.9, DMSO) versus N ‐Boc‐benzylamine (p K a =22.9, DMSO); the stronger acid possesses a less electron‐rich nitrogen atom. See: | en_US |
dc.identifier.citedreference | J. P. Cheng, M. Xian, K. Wang, X. Zhu, Z. Yin, P. G. Wang, J. Am. Chem. Soc. 1998, 120, 10266 – 10267; | en_US |
dc.identifier.citedreference | T. Mita, J. Chen, M. Sugawara, Y. Sato, Angew. Chem. 2011, 123, 1429 – 1432; Angew. Chem. Int. Ed. 2011, 50, 1393 – 1396. | en_US |
dc.identifier.citedreference | The syn ‐aminopalladation of N ‐aryl‐pent‐4‐enylamines has been shown to be irreversible in Pd/dppf complexes. [16c] Related migratory insertions of ethylene into LPd‐NPh 2 complexes have also been shown to be irreversible. [16b,d] The p K a of diphenylamine (25.0) is comparable to that of N ‐Boc‐benzylamine. See: J. N. Li, L. Liu, Y. Fu, Q. X. Guo, Tetrahedron 2006, 62, 4453 – 4462. | en_US |
dc.identifier.citedreference | The observation that deuterated urea substrate ( Z )‐[D]‐1 f is converted to a 7:1 mixture of diastereomers whereas the analogous deuterated carbamate is transformed with >20:1 d.r. is consistent with relatively fast reductive elimination in the carbamate system as compared to the urea. See: | en_US |
dc.identifier.citedreference | Ref. [12]; | en_US |
dc.identifier.citedreference | M. B. Bertrand, J. D. Neukom, J. P. Wolfe, J. Org. Chem. 2008, 73, 8851 – 8860. | en_US |
dc.identifier.citedreference | en_US | |
dc.identifier.citedreference | For a review on the effects of anionic ligands in catalytic asymmetric reactions, see: K. Fagnou, M. Lautens, Angew. Chem. 2002, 114, 26 – 49; Angew. Chem. Int. Ed. 2002, 41, 26 – 47; | en_US |
dc.identifier.citedreference | for a review on the effect of anionic ligands on Pd‐catalyzed asymmetric allylation reactions, see: B. M. Trost, T. Zhang, J. D. Sieber, Chem. Sci. 2010, 1, 427 – 440. | en_US |
dc.identifier.citedreference | Small anionic ligands increase the rate of CC bond‐forming reductive elimination from five‐coordinate L 2 Pd(Ar)(Ar 1 ) complexes. However, a small anionic ligand (Cl − ) has been shown to dramatically decrease the rate of CC bond‐forming reductive elimination from four ‐ coordinate anionic L 1 Pd II (aryl)(alkyl) complexes related to 10 and 11. See: | en_US |
dc.identifier.citedreference | B. Pudasaini, B. G. Janesko, Organometallics 2011, 30, 4564 – 4571; | en_US |
dc.identifier.citedreference | C. Amatore, A. Jutand, G. Le Duc, Chem. Eur. J. 2011, 17, 2492 – 2503. | en_US |
dc.identifier.citedreference | For a review, see: J. F. Hartwig, Inorg. Chem. 2007, 46, 1936 – 1947. | en_US |
dc.identifier.citedreference | en_US | |
dc.identifier.citedreference | J. Dumas, Curr. Opin. Drug Discovery Dev. 2002, 5, 718 – 727; | en_US |
dc.identifier.citedreference | E. DeClercq, Biochem. Biophys. Acta. 2002, 1587, 258 – 275; | en_US |
dc.identifier.citedreference | W. M. Kazmierski, E. Furfine, Y. Gray‐Nunez, A. Spaltenstein, L. Wright, Bioorg. Med. Chem. Lett. 2004, 14, 5685 – 5687. | en_US |
dc.identifier.citedreference | For other catalytic asymmetric syntheses of imidazolidin‐2‐ones, see: | en_US |
dc.identifier.citedreference | H. Du, B. Zhao, W. Yuan, Y. Shi, Org. Lett. 2008, 10, 4231 – 4234; | en_US |
dc.identifier.citedreference | H. Du, B. Zhao, Y. Shi, J. Am. Chem. Soc. 2008, 130, 8590 – 8591; | en_US |
dc.identifier.citedreference | B. Zhao, H. Du, Y. Shi, J. Org. Chem. 2009, 74, 4411 – 4413; | en_US |
dc.identifier.citedreference | B. M. Trost, D. R. Fandrick, J. Am. Chem. Soc. 2003, 125, 11836 – 11837. | en_US |
dc.identifier.citedreference | G. Sartori, R. Maggi in Science of Synthesis (Houben‐Weyl Methods of Molecular Transformations) Vol. 18 (Eds.: S. V. Ley, J. G. Knight ), Thieme, Stuttgart, 2005, pp. 665 – 758. | en_US |
dc.identifier.citedreference | D. Lucet, T. L. Gall, C. Mioskowski, Angew. Chem. 1998, 110, 2724 – 2772; Angew. Chem. Int. Ed. 1998, 37, 2580 – 2627. | en_US |
dc.identifier.citedreference | For the synthesis of racemic ureas by Pd‐catalyzed alkene carboamination, see: | en_US |
dc.identifier.citedreference | J. A. Fritz, J. S. Nakhla, J. P. Wolfe, Org. Lett. 2006, 8, 2531 – 2534; | en_US |
dc.identifier.citedreference | J. A. Fritz, J. P. Wolfe, Tetrahedron 2008, 64, 6838 – 6852. | en_US |
dc.identifier.citedreference | For recent reviews on Pd‐catalyzed alkene carboamination reactions, see: | en_US |
dc.identifier.citedreference | D. M. Schultz, J. P. Wolfe, Synthesis 2012, 351 – 361; | en_US |
dc.identifier.citedreference | J. P. Wolfe, Synlett 2008, 2913 – 2937. | en_US |
dc.identifier.citedreference | en_US | |
dc.identifier.citedreference | D. N. Mai, J. P. Wolfe, J. Am. Chem. Soc. 2010, 132, 12157 – 12159; | en_US |
dc.identifier.citedreference | T. W. Liwosz, S. R. Chemler, J. Am. Chem. Soc. 2012, 134, 2020 – 2023; | en_US |
dc.identifier.citedreference | W. Zeng, S. R. Chemler, J. Am. Chem. Soc. 2007, 129, 12948 – 12949; | en_US |
dc.identifier.citedreference | S. R. Chemler, Org. Biomol. Chem. 2009, 7, 3009 – 3019. | en_US |
dc.identifier.citedreference | X. X. Guo, J. H. Xie, G. H. Hou, W. J. Shi, L. X. Wang, Q. L. Zhou, Tetrahedron: Asymmetry 2004, 15, 2231 – 2234. | en_US |
dc.identifier.citedreference | Use of ( R )‐Siphos‐PE as the ligand led to formation of ( R )‐ 2 b in 25 % ee. | en_US |
dc.identifier.citedreference | Replacement of the substrate N ‐methyl group with other substituents such as benzyl or p ‐methoxyphenyl did not lead to improved enantioselectivities. | en_US |
dc.identifier.citedreference | A similar effect was observed when substoichiometric amounts (50 mol %) of water or NaOH were added. However, the highest degree of reproducibility was obtained with 2.0 equiv of added water. | en_US |
dc.identifier.citedreference | The minor diastereomer likely arises through reversible β‐hydride elimination/reinsertion pathways. For further details, see: M. B. Hay, J. P. Wolfe, J. Am. Chem. Soc. 2005, 127, 16468 – 16476. Additional details are also provided in the Supporting Information. | en_US |
dc.identifier.citedreference | D. N. Mai, Ph.D. Thesis, University of Michigan, Ann Arbor, MI, 2011. | en_US |
dc.identifier.citedreference | en_US | |
dc.identifier.citedreference | R. A. Fernandes, A. Stimac, Y. Yamamoto, J. Am. Chem. Soc. 2003, 125, 14133 – 14139; | en_US |
dc.owningcollname | Interdisciplinary and Peer-Reviewed |
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