Investigation of cis- and trans-4-Fluoroprolines as Enantioselective Catalysts in a Variety of Organic Transformations
Daryl Q. J. Yap A , Raju Cheerlavancha A , Renecia Lowe A , Siyao Wang A and Luke Hunter A B
+ Author Affiliations
- Author Affiliations
A School of Chemistry, University of New South Wales, Sydney, NSW 2052, Australia.
B Corresponding author. Email: l.hunter@unsw.edu.au
Australian Journal of Chemistry 68(1) 44-49 https://doi.org/10.1071/CH14129
Submitted: 10 March 2014 Accepted: 12 April 2014 Published: 21 May 2014
Abstract
Stereoselective fluorination is known to rigidify the ring structure of l-proline, as a result of a combination of electrostatic and hyperconjugative effects associated with the C–F bond. This is a potential strategy for enhancing the enantioselectivity of proline-catalysed reactions. In this study, cis- and trans-4-fluoroprolines were investigated as catalysts in five different organic transformations, including examples of both enamine and iminium ion catalysis. Some significant differences in enantioselectivity were observed between the cis- and trans-isomers of the fluorinated catalysts, confirming that the ring pucker is important. However, no substantial improvements were observed relative to the parent catalyst, l-proline.
References
[1] D. W. MacMillan, Nature 2008, 455, 304.| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXhtFams7zJ&md5=ad377422096b1fd458447d98c7fccedcCAS | 18800128PubMed |
[2] B. List, R. A. Lerner, C. F. Barbas, J. Am. Chem. Soc. 2000, 122, 2395.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3cXhtlGqurk%3D&md5=b7cdbcdd299a703d501f63723520421cCAS |
[3] K. A. Ahrendt, C. J. Borths, D. W. MacMillan, J. Am. Chem. Soc. 2000, 122, 4243.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3cXisVGjurw%3D&md5=1ffb040dcbc4adf3464680eabfdd31b5CAS |
[4] Z. G. Hajos, D. R. Parrish, J. Org. Chem. 1974, 39, 1615.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaE2cXkvFWisrY%3D&md5=f9579867ff0fd91b58d661812c37a55dCAS |
[5] T. Bui, C. F. Barbas, Tetrahedron Lett. 2000, 41, 6951.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3cXmtF2isro%3D&md5=d64520c7507827c02aa103b4f949fd99CAS |
[6] B. List, J. Am. Chem. Soc. 2000, 122, 9336.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3cXmt1WitL8%3D&md5=4aa97c34188643c29540104178825abeCAS |
[7] S. Hanessian, V. Pham, Org. Lett. 2000, 2, 2975.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3cXlslChtLs%3D&md5=280bc2553e5173e01cb7f6a3b65a3df4CAS | 10986086PubMed |
[8] N. M. Elnagdi, N. S. Al-Hokbany, Molecules 2012, 17, 4300.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38XmtFCqsrs%3D&md5=80f891ca7029c5af4f1ba07518208394CAS | 22491679PubMed |
[9] L. Hunter, Beilstein J. Org. Chem. 2010, 6, 1.
| Crossref | GoogleScholarGoogle Scholar |
[10] X.-G. Hu, L. Hunter, Beilstein J. Org. Chem. 2013, 9, 2696.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2cXisFCru7g%3D&md5=a999f14b8eb660bbe8af48c9ffef6dd1CAS | 24367435PubMed |
[11] (a) K. B. Wiberg, M. A. Murcko, K. E. Laidig, P. J. MacDougall, J. Phys. Chem. 1990, 94, 6956.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK3cXltlWgsrs%3D&md5=9f7f2a79e2989bb5a52137be9e744279CAS |
(b) D. O’Hagan, C. Bilton, J. A. K. Howard, L. Knight, D. J. Tozer, J. Chem. Soc., Perkin Trans. 2 2000, 605.
| Crossref | GoogleScholarGoogle Scholar |
(c) C. R. Briggs, D. O’Hagan, H. S. Rzepa, A. M. Z. Slawin, J. Fluor. Chem. 2004, 125, 19.
| Crossref | GoogleScholarGoogle Scholar |
[12] (a) A. M. Sun, D. C. Lankin, K. Hardcastle, J. P. Snyder, Chem. – Eur. J. 2005, 11, 1579.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD2MXitVOmtLc%3D&md5=8870607a61c42340f27437b7a56c844bCAS |
(b) C. R. Briggs, M. J. Allen, D. O’Hagan, D. J. Tozer, A. M. Z. Slawin, A. E. Goeta, J. A. K. Howard, Org. Biomol. Chem. 2004, 2, 732.
| Crossref | GoogleScholarGoogle Scholar |
(c) N. E. J. Gooseman, D. O’Hagan, M. J. G. Peach, A. M. Z. Slawin, D. J. Tozer, R. J. Young, Angew. Chem. Int. Ed. 2007, 46, 5904.
| Crossref | GoogleScholarGoogle Scholar |
[13] (a) D. B. Hobart, J. S. Merola, Acta Crystallogr. E 2012, 68, o2490.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC38XhtFCju7jF&md5=cf8e74e5bd9c5ed6aaac8e704b4e34b4CAS |
(b) S. K. Holmgren, L. E. Bretscher, K. M. Taylor, R. T. Raines, Chem. Biol. 1999, 6, 63.
| Crossref | GoogleScholarGoogle Scholar |
[14] J. Díaz, J. M. Goodman, Tetrahedron 2010, 66, 8021.
| Crossref | GoogleScholarGoogle Scholar |
[15] D. A. Bock, C. W. Lehmann, B. List, Proc. Natl. Acad. Sci. USA 2010, 107, 20636.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXhsFejtrrK&md5=c9ce535ebbbbdd0a43bdf51899109b42CAS | 21068369PubMed |
[16] Y. P. Rey, L. E. Zimmer, C. Sparr, E.-M. Tanzer, W. B. Schweizer, H. M. Senn, S. Lakhdar, R. Gilmour, Eur. J. Org. Chem. 2014, 1202.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2cXltVyiug%3D%3D&md5=a1e018aa99e9df589d51cc96f4244114CAS |
[17] L. E. Zimmer, C. Sparr, R. Gilmour, Angew. Chem. Int. Ed. 2011, 50, 11860.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3MXht1Wrs7%2FF&md5=997475da97059da14de097c517be273fCAS |
[18] (a) C. M. Marson, R. C. Melling, Chem. Commun. 1998, 1223.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaK1cXjtlaqu7o%3D&md5=963c34d7746959fa2fff3013bc2a535aCAS |
(b) C. M. Marson, R. C. Melling, J. Org. Chem. 2005, 70, 9771.
| Crossref | GoogleScholarGoogle Scholar |
[19] C. Sparr, R. Gilmour, Angew. Chem. Int. Ed. 2010, 49, 6520.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3cXhtFamur3M&md5=30df58b48c4d14ce27c630eeca34a6b6CAS |
[20] (a) C. Sparr, W. B. Schweizer, H. M. Senn, R. Gilmour, Angew. Chem. Int. Ed. 2009, 48, 3065.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXltVyit7Y%3D&md5=347305c023002b2790b6f0f8f1178a8eCAS |
(b) I. G. Molnár, E.-M. Tanzer, C. Daniliuc, R. Gilmour, Chem. – Eur. J. 2014, 20, 794.
| Crossref | GoogleScholarGoogle Scholar |
[21] D. A. DiRocco, K. M. Oberg, D. M. Dalton, T. Rovis, J. Am. Chem. Soc. 2009, 131, 10872.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1MXos1ehsrs%3D&md5=ec859eb55e68f932ddce26d7ae4a2db0CAS | 19722669PubMed |
[22] Y. P. Rey, R. Gilmour, Beilstein J. Org. Chem. 2013, 9, 2812.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC2cXisFCru7k%3D&md5=a86754be25b78bb0276846afa876e4a1CAS | 24367445PubMed |
[23] C. L. Chandler, B. List, J. Am. Chem. Soc. 2008, 130, 6737.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXlsVKmtbY%3D&md5=d67991e17d4481d288bf68d0139e5e9cCAS | 18454521PubMed |
[24] M. S. Chorghade, D. K. Mohapatra, G. Sahoo, M. K. Gurjar, M. V. Mandlecha, N. Bhoite, S. Moghe, R. T. Raines, J. Fluor. Chem. 2008, 129, 781.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXhtVyitrbM&md5=6f7989186fe83183cce4bbd66aa121d7CAS | 19727323PubMed |
[25] See Supplementary Material.
[26] Z.-X. Du, L.-Y. Zhang, X.-Y. Fan, F.-C. Wu, C.-S. Da, Tetrahedron Lett. 2013, 54, 2828.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3sXmt1Wht7Y%3D&md5=17d0ede5305ea745016e7a937da89fc3CAS |
[27] K. Sakthivel, W. Notz, T. Bui, C. F. Barbas, J. Am. Chem. Soc. 2001, 123, 5260.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD3MXjt1Oisrw%3D&md5=dcb932f2b57c9607424bce54cbb8c48eCAS | 11457388PubMed |
[28] P. Buchschacher, A. Fürst, J. Gutzwiller, Org. Synth. 1985, 63, 37.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DyaL28XovVagsA%3D%3D&md5=8877495c6bc2310afe3121e4882edfe5CAS |
[29] R. Pedrosa, J. M. Andrés, R. Manzano, C. Pérez-López, Tetrahedron Lett. 2013, 54, 3101.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BC3sXmvV2hs78%3D&md5=fabbe5eafc3cbe5d0baa91ac9bed88a1CAS |
[30] S. V. Pansare, R. Lingampally, Org. Biomol. Chem. 2009, 7, 319.
| Crossref | GoogleScholarGoogle Scholar | 1:CAS:528:DC%2BD1cXhsFemurbJ&md5=a64732b60691734b9fc1dfa00013be0cCAS | 19109677PubMed |
