Enantioselective Synthesis of Piperidines through the Formation of Chiral Mixed Phosphoric Acid Acetals: Experimental and Theoretical Studies
dc.contributor.author | Sun, Zhankui | en_US |
dc.contributor.author | Winschel, Grace A. | en_US |
dc.contributor.author | Zimmerman, Paul M. | en_US |
dc.contributor.author | Nagorny, Pavel | en_US |
dc.date.accessioned | 2014-11-04T16:35:56Z | |
dc.date.available | WITHHELD_12_MONTHS | en_US |
dc.date.available | 2014-11-04T16:35:56Z | |
dc.date.issued | 2014-10-13 | en_US |
dc.identifier.citation | Sun, Zhankui; Winschel, Grace A.; Zimmerman, Paul M.; Nagorny, Pavel (2014). "Enantioselective Synthesis of Piperidines through the Formation of Chiral Mixed Phosphoric Acid Acetals: Experimental and Theoretical Studies ." Angewandte Chemie International Edition 53(42): 11194-11198. | en_US |
dc.identifier.issn | 1433-7851 | en_US |
dc.identifier.issn | 1521-3773 | en_US |
dc.identifier.uri | https://hdl.handle.net/2027.42/109355 | |
dc.description.abstract | An enantioselective intramolecular chiral phosphoric acid‐catalyzed cyclization of unsaturated acetals has been utilized for the synthesis of functionalized chiral piperidines. The chiral enol ether products of these cyclizations undergo subsequent in situ enantioenrichment through acetalization of the minor enantiomer. A new computational reaction exploration method was utilized to elucidate the mechanism and stereoselectivity of this transformation. Rather than confirming the originally postulated cyclization proceeding directly through a vinyl oxocarbenium ion, simulations identified an alternative two‐step mechanism involving the formation of a mixed chiral phosphate acetal, which undergoes a concerted, asynchronous S N 2′‐like displacement to yield the product with stereoselectivity in agreement with experimental observations. A rich seam : An enantioselective chiral phosphoric acid‐catalyzed cyclization of unsaturated acetals has been utilized for the synthesis of functionalized chiral piperidines. The chiral enol ether products of these cyclizations undergo subsequent in situ enantioenrichment. A new computational method was utilized to elucidate the mechanism and stereoselectivity of this transformation. Cbz=benzyloxycarbonyl; S =resolution. | en_US |
dc.publisher | WILEY‐VCH Verlag | en_US |
dc.subject.other | Heterocycles | en_US |
dc.subject.other | Density Functional Calculations | en_US |
dc.subject.other | Asymmetric Catalysis | en_US |
dc.subject.other | Organocatalysis | en_US |
dc.subject.other | Transition States | en_US |
dc.title | Enantioselective Synthesis of Piperidines through the Formation of Chiral Mixed Phosphoric Acid Acetals: Experimental and Theoretical Studies | 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, Ann Arbor, MI 48109 (USA) | en_US |
dc.description.bitstreamurl | http://deepblue.lib.umich.edu/bitstream/2027.42/109355/1/anie_201405128_sm_miscellaneous_information.pdf | |
dc.description.bitstreamurl | http://deepblue.lib.umich.edu/bitstream/2027.42/109355/2/11194_ftp.pdf | |
dc.identifier.doi | 10.1002/anie.201405128 | en_US |
dc.identifier.source | Angewandte Chemie International Edition | en_US |
dc.identifier.citedreference | E. C. Carlson, L. K. Rathbone, H. Yang, N. D. Collett, R. G. Carter, J. Org. Chem. 2008, 73, 5155; | en_US |
dc.identifier.citedreference | A. Borovika, P.‐I. Tang, S. Klapman, P. Nagorny, Angew. Chem. Int. Ed. 2013, 52, 13424; Angew. Chem. 2013, 125, 13666. | en_US |
dc.identifier.citedreference | en_US | |
dc.identifier.citedreference | K. Takasu, S. Maiti, M. Ihara, Heterocycles 2003, 59, 51; | en_US |
dc.identifier.citedreference | S. Fustero, D. Jimenez, J. Moscardo, S. Catalan, C. del Pozo, Org. Lett. 2007, 9, 5283; | en_US |
dc.identifier.citedreference | S.‐L. You, Z. Feng, Q.‐L. Xu, L.‐X. Dai, Heterocycles 2010, 80, 765; | en_US |
dc.identifier.citedreference | J.‐D. Liu, Y.‐C. Chen, G.‐B. Zhang, Z.‐Q. Li, P. Chen, J.‐Y. Du, Y.‐Q. Tu, C.‐A. Fan, Adv. Synth. Catal. 2011, 353, 2721; | en_US |
dc.identifier.citedreference | T. Cheng, S. Meng, Y. Huang, Org. Lett. 2013, 15, 1958; | en_US |
dc.identifier.citedreference | R. Miyaji, K. Asano, S. Matsubara, Org. Lett. 2013, 15, 3658; | en_US |
dc.identifier.citedreference | N. Veerasamy, E. C. Carlson, N. D. Collett, M. Saha, R. G. Carter, J. Org. Chem. 2013, 78, 4779; | en_US |
dc.identifier.citedreference | Y. Fukata, K. Asano, S. Matsubara, Chem. Lett. 2013, 42, 355. | en_US |
dc.identifier.citedreference | Reviews: | en_US |
dc.identifier.citedreference | C. F. Nising, S. Brase, Chem. Soc. Rev. 2008, 37, 1218; | en_US |
dc.identifier.citedreference | Z. Amara, J. Caron, D. Joseph, Nat. Prod. Rep. 2013, 30, 1211. | en_US |
dc.identifier.citedreference | Y. Ying, H. Kim, J. Hong, Org. Lett. 2011, 13, 796. | en_US |
dc.identifier.citedreference | Note that the protonated 14 and 15 are not identified as stable structures. Optimization of the structures 14 and 15 led to 1 a and 5 a, respectively, thus indicating these are not stationary points on the PES. For the potential energy surface for the formation of the minor enantiomer refer to Schemes SI–SIII. | en_US |
dc.identifier.citedreference | The transition‐states 11 and 12 could be distinguished by the change in the charge distribution as well as by the PO‐C distances. Refer to the Supporting Information (p. 21) for a more detailed discussion. | en_US |
dc.identifier.citedreference | en_US | |
dc.identifier.citedreference | P. M. Zimmerman, J. Comput. Chem. 2013, 34, 1385; | en_US |
dc.identifier.citedreference | P. M. Zimmerman, J. Chem. Phys. 2013, 138, 184102; | en_US |
dc.identifier.citedreference | P. M. Zimmerman, J. Chem. Theory Comput. 2013, 9, 3043. | en_US |
dc.identifier.citedreference | A. V. Marenich, C. J. Cramer, D. G. Truhlar, J. Phys. Chem. B 2009, 113, 6378. | en_US |
dc.identifier.citedreference | N. D. Shapiro, V. Rauniyar, G. L. Hamilton, J. Wu, F. D. Toste, Nature 2011, 470, 245. | en_US |
dc.identifier.citedreference | en_US | |
dc.identifier.citedreference | A. Wassermann, J. Chem. Soc. 1942, 618; | en_US |
dc.identifier.citedreference | P. Yates, P. Eaton, J. Am. Chem. Soc. 1960, 82, 4436. | en_US |
dc.identifier.citedreference | Selected reviews: | en_US |
dc.identifier.citedreference | N. N. Joshi, Proc. Indian Natl. Sci. Acad. 2002, 68, 435; | en_US |
dc.identifier.citedreference | A. Corma, H. Garcia, Chem. Rev. 2003, 103, 4307; | en_US |
dc.identifier.citedreference | A. G. Doyle, E. N. Jacobsen, Chem. Rev. 2007, 107, 5713; | en_US |
dc.identifier.citedreference | M. Rueping, A. Kuenkel, I. Atodiresei, Chem. Soc. Rev. 2011, 40, 4539; | en_US |
dc.identifier.citedreference | G. Lelais, D. W. C. MacMillan, Aldrichimica Acta 2006, 39, 79; | en_US |
dc.identifier.citedreference | D. W. C. MacMillan, Nature 2008, 455, 304; | en_US |
dc.identifier.citedreference | A. Erkkilä, I. Majander, P. M. Pihko, Chem. Rev. 2007, 107, 5416. | en_US |
dc.identifier.citedreference | M. Harmata, P. Rashatasakhon, Tetrahedron 2003, 59, 2371. | en_US |
dc.identifier.citedreference | Auxiliary‐controlled ionic [2+4] cycloadditions: | en_US |
dc.identifier.citedreference | T. Sammakia, M. A. Berliner, J. Org. Chem. 1994, 59, 6890; | en_US |
dc.identifier.citedreference | T. Sammakia, M. A. Berliner, J. Org. Chem. 1995, 60, 6652; | en_US |
dc.identifier.citedreference | A. Haudrechy, W. Picoul, Y. Langlois, Tetrahedron: Asymmetry 1997, 8, 139; | en_US |
dc.identifier.citedreference | R. Kumareswaran, P. S. Vankar, M. V. R. Reddy, S. V. Pitre, R. Roy, Y. D. Vankar, Tetrahedron 1999, 55, 1099. | en_US |
dc.identifier.citedreference | Auxiliary‐controlled ionic [3+4] cycloadditions: | en_US |
dc.identifier.citedreference | M. Harmata, D. E. Jones, J. Org. Chem. 1997, 62, 1578; | en_US |
dc.identifier.citedreference | M. Harmata, D. E. Jones, M. Kahraman, U. Sharma, C. L. Barnes, Tetrahedron Lett. 1999, 40, 1831; | en_US |
dc.identifier.citedreference | C. B. W. Stark, U. Eggert, H. M. R. Hoffmann, Angew. Chem. Int. Ed. 1998, 37, 1266; Angew. Chem. 1998, 110, 1337. | en_US |
dc.identifier.citedreference | en_US | |
dc.identifier.citedreference | M. Terada, H. Tanaka, K. Sorimachi, J. Am. Chem. Soc. 2009, 131, 3430; | en_US |
dc.identifier.citedreference | I. Čorić, S. Vellalath, B. List, J. Am. Chem. Soc. 2010, 132, 8536; | en_US |
dc.identifier.citedreference | D. J. Cox, M. D. Smith, A. J. Fairbanks, Org. Lett. 2010, 12, 1452; | en_US |
dc.identifier.citedreference | I. Čorić, S. Müller, B. List, J. Am. Chem. Soc. 2010, 132, 17370; | en_US |
dc.identifier.citedreference | Z.‐Y. Han, R. Guo, P.‐S. Wang, D.‐F. Chen, H. Xiao, L.‐Z. Gong, Tetrahedron Lett. 2011, 52, 5963; | en_US |
dc.identifier.citedreference | I. Čorić, B. List, Nature 2012, 483, 315; | en_US |
dc.identifier.citedreference | Z. Sun, G. A. Winschel, A. Borovika, P. Nagorny, J. Am. Chem. Soc. 2012, 134, 8074; | en_US |
dc.identifier.citedreference | M. Terada, Y. Toda, Angew. Chem. Int. Ed. 2012, 51, 2093; Angew. Chem. 2012, 124, 2135; | en_US |
dc.identifier.citedreference | H. Wu, Y.‐P. He, L.‐Z. Gong, Org. Lett. 2013, 15, 460; | en_US |
dc.identifier.citedreference | J. H. Kim, I. Coric, S. Vellalath, B. List, Angew. Chem. Int. Ed. 2013, 52, 4474; Angew. Chem. 2013, 125, 4474; | en_US |
dc.identifier.citedreference | E. Mensah, N. Camasso, W. Kaplan, P. Nagorny, Angew. Chem. Int. Ed. 2013, 52, 12932; Angew. Chem. 2013, 125, 13170; | en_US |
dc.identifier.citedreference | P. Nagorny, Z. Sun, G. Winschel, Synlett 2013, 661; | en_US |
dc.identifier.citedreference | T. Kimura, M. Sekine, D. Takahashi, K. Toshima, Angew. Chem. Int. Ed. 2013, 52, 12131; Angew. Chem. 2013, 125, 12353; | en_US |
dc.identifier.citedreference | Z. Chen, J. Sun, Angew. Chem. Int. Ed. 2013, 52, 13593; Angew. Chem. 2013, 125, 13838; | en_US |
dc.identifier.citedreference | C.‐C. Hsiao, H.‐H. Liao, E. Sugiono, I. Atodiresei, M. Rueping, Chem. Eur. J. 2013, 19, 9775; | en_US |
dc.identifier.citedreference | M. Terada, T. Yamanaka, Y. Toda, Chem. Eur. J. 2013, 19, 13658; | en_US |
dc.identifier.citedreference | R. Quach, D. P. Furket, M. A. Brimble, Tetrahedron Lett. 2013, 54, 5865; | en_US |
dc.identifier.citedreference | Y. Cui, L. A. Villafane, D. J. Clausen, P. E. Floreancig, Tetrahedron 2013, 69, 7618; | en_US |
dc.identifier.citedreference | C. Lu, X. Su, P. E. Floreancig, J. Org. Chem. 2013, 78, 9366; | en_US |
dc.identifier.citedreference | V. M. Lombardo, C. D. Thomas, K. A. Scheidt, Angew. Chem. Int. Ed. 2013, 52, 12910; Angew. Chem. 2013, 125, 13148. | en_US |
dc.identifier.citedreference | en_US | |
dc.identifier.citedreference | A. Borovika, P. Nagorny, Tetrahedron 2013, 69, 5719; | en_US |
dc.owningcollname | Interdisciplinary and Peer-Reviewed |
Files in this item
Remediation of Harmful Language
The University of Michigan Library aims to describe library materials in a way that respects the people and communities who create, use, and are represented in our collections. Report harmful or offensive language in catalog records, finding aids, or elsewhere in our collections anonymously through our metadata feedback form. More information at Remediation of Harmful Language.
Accessibility
If you are unable to use this file in its current format, please select the Contact Us link and we can modify it to make it more accessible to you.