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Synthesis of Enantiomerically Enriched Imidazolidin‐2‐Ones through Asymmetric Palladium‐Catalyzed Alkene Carboamination Reactions
dc.contributor.authorHopkins, Brett A.en_US
dc.contributor.authorWolfe, John P.en_US
dc.date.accessioned2012-10-02T17:19:58Z
dc.date.available2013-10-18T17:47:30Zen_US
dc.date.issued2012-09-24en_US
dc.identifier.citationHopkins, 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.issn1433-7851en_US
dc.identifier.issn1521-3773en_US
dc.identifier.urihttps://hdl.handle.net/2027.42/93659
dc.publisherWILEY‐VCH Verlagen_US
dc.subject.otherStereoselectivityen_US
dc.subject.otherPalladiumen_US
dc.subject.otherHeterocyclesen_US
dc.subject.otherAsymmetric Catalysisen_US
dc.subject.otherAsymmetric Synthesisen_US
dc.titleSynthesis of Enantiomerically Enriched Imidazolidin‐2‐Ones through Asymmetric Palladium‐Catalyzed Alkene Carboamination Reactionsen_US
dc.typeArticleen_US
dc.rights.robotsIndexNoFollowen_US
dc.subject.hlbsecondlevelChemistryen_US
dc.subject.hlbtoplevelScienceen_US
dc.description.peerreviewedPeer Revieweden_US
dc.contributor.affiliationumDepartment of Chemistry, University of Michigan, 930 N. University Ave, Ann Arbor, MI 48109‐1055 (USA)en_US
dc.contributor.affiliationumDepartment of Chemistry, University of Michigan, 930 N. University Ave, Ann Arbor, MI 48109‐1055 (USA)en_US
dc.identifier.pmid22936415en_US
dc.description.bitstreamurlhttp://deepblue.lib.umich.edu/bitstream/2027.42/93659/1/9886_ftp.pdf
dc.description.bitstreamurlhttp://deepblue.lib.umich.edu/bitstream/2027.42/93659/2/anie_201205233_sm_miscellaneous_information.pdf
dc.identifier.doi10.1002/anie.201205233en_US
dc.identifier.sourceAngewandte Chemie International Editionen_US
dc.identifier.citedreferenceP. B. White, S. S. Stahl, J. Am. Chem. Soc. 2011, 133, 18594 – 18597.en_US
dc.identifier.citedreferenceS. Rousseaux, J. Garcia‐Fortanet, M. A. Del Aguila Sanchez, S. L. Buchwald, J. Am. Chem. Soc. 2011, 133, 9282 – 9285.en_US
dc.identifier.citedreferenceIn 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.citedreferenceFor studies on the mechanism of syn ‐migratory insertion of alkenes into PdN bonds, see:en_US
dc.identifier.citedreferenceJ. D. Neukom, N. S. Perch, J. P. Wolfe, J. Am. Chem. Soc. 2010, 132, 6276 – 6277;en_US
dc.identifier.citedreferenceP. S. Hanley, D. Markovic, J. F. Hartwig, J. Am. Chem. Soc. 2010, 132, 6302 – 6303;en_US
dc.identifier.citedreferenceJ. D. Neukom, N. S. Perch, J. P. Wolfe, Organometallics 2011, 30, 1269 – 1277;en_US
dc.identifier.citedreferenceP. S. Hanley, J. F. Hartwig, J. Am. Chem. Soc. 2011, 133, 15661 – 15673;en_US
dc.identifier.citedreferenceOur 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.citedreferenceJ. 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.citedreferenceT. 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.citedreferenceThe 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.citedreferenceThe 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.citedreferenceRef. [12];en_US
dc.identifier.citedreferenceM. B. Bertrand, J. D. Neukom, J. P. Wolfe, J. Org. Chem. 2008, 73, 8851 – 8860.en_US
dc.identifier.citedreference en_US
dc.identifier.citedreferenceFor 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.citedreferencefor 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.citedreferenceSmall anionic ligands increase the rate of CC 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 CC 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.citedreferenceB. Pudasaini, B. G. Janesko, Organometallics 2011, 30, 4564 – 4571;en_US
dc.identifier.citedreferenceC. Amatore, A. Jutand, G. Le Duc, Chem. Eur. J. 2011, 17, 2492 – 2503.en_US
dc.identifier.citedreferenceFor a review, see: J. F. Hartwig, Inorg. Chem. 2007, 46, 1936 – 1947.en_US
dc.identifier.citedreference en_US
dc.identifier.citedreferenceJ. Dumas, Curr. Opin. Drug Discovery Dev. 2002, 5, 718 – 727;en_US
dc.identifier.citedreferenceE. DeClercq, Biochem. Biophys. Acta. 2002, 1587, 258 – 275;en_US
dc.identifier.citedreferenceW. M. Kazmierski, E. Furfine, Y. Gray‐Nunez, A. Spaltenstein, L. Wright, Bioorg. Med. Chem. Lett. 2004, 14, 5685 – 5687.en_US
dc.identifier.citedreferenceFor other catalytic asymmetric syntheses of imidazolidin‐2‐ones, see:en_US
dc.identifier.citedreferenceH. Du, B. Zhao, W. Yuan, Y. Shi, Org. Lett. 2008, 10, 4231 – 4234;en_US
dc.identifier.citedreferenceH. Du, B. Zhao, Y. Shi, J. Am. Chem. Soc. 2008, 130, 8590 – 8591;en_US
dc.identifier.citedreferenceB. Zhao, H. Du, Y. Shi, J. Org. Chem. 2009, 74, 4411 – 4413;en_US
dc.identifier.citedreferenceB. M. Trost, D. R. Fandrick, J. Am. Chem. Soc. 2003, 125, 11836 – 11837.en_US
dc.identifier.citedreferenceG. 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.citedreferenceD. Lucet, T. L. Gall, C. Mioskowski, Angew. Chem. 1998, 110, 2724 – 2772; Angew. Chem. Int. Ed. 1998, 37, 2580 – 2627.en_US
dc.identifier.citedreferenceFor the synthesis of racemic ureas by Pd‐catalyzed alkene carboamination, see:en_US
dc.identifier.citedreferenceJ. A. Fritz, J. S. Nakhla, J. P. Wolfe, Org. Lett. 2006, 8, 2531 – 2534;en_US
dc.identifier.citedreferenceJ. A. Fritz, J. P. Wolfe, Tetrahedron 2008, 64, 6838 – 6852.en_US
dc.identifier.citedreferenceFor recent reviews on Pd‐catalyzed alkene carboamination reactions, see:en_US
dc.identifier.citedreferenceD. M. Schultz, J. P. Wolfe, Synthesis 2012, 351 – 361;en_US
dc.identifier.citedreferenceJ. P. Wolfe, Synlett 2008, 2913 – 2937.en_US
dc.identifier.citedreference en_US
dc.identifier.citedreferenceD. N. Mai, J. P. Wolfe, J. Am. Chem. Soc. 2010, 132, 12157 – 12159;en_US
dc.identifier.citedreferenceT. W. Liwosz, S. R. Chemler, J. Am. Chem. Soc. 2012, 134, 2020 – 2023;en_US
dc.identifier.citedreferenceW. Zeng, S. R. Chemler, J. Am. Chem. Soc. 2007, 129, 12948 – 12949;en_US
dc.identifier.citedreferenceS. R. Chemler, Org. Biomol. Chem. 2009, 7, 3009 – 3019.en_US
dc.identifier.citedreferenceX. 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.citedreferenceUse of ( R )‐Siphos‐PE as the ligand led to formation of ( R )‐ 2 b in 25 % ee.en_US
dc.identifier.citedreferenceReplacement 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.citedreferenceA 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.citedreferenceThe 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.citedreferenceD. N. Mai, Ph.D. Thesis, University of Michigan, Ann Arbor, MI, 2011.en_US
dc.identifier.citedreference en_US
dc.identifier.citedreferenceR. A. Fernandes, A. Stimac, Y. Yamamoto, J. Am. Chem. Soc. 2003, 125, 14133 – 14139;en_US
dc.owningcollnameInterdisciplinary and Peer-Reviewed


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