Journal of the American Chemical Society
Communication
(5) For enzyme and metal complex cocatalyzed dynamic kinetic
principle for the general concept of catalyzing amine-carbonyl
condensations enantioselectively, a concept which we assume
to be widely applicable to many other transformations. Our
methodology tolerates a wide variety of amines, and most
remarkably, even aliphatic amines are resolved with good to
excellent selectivity. Currently, we can only speculate on the
origin of enantioselectivity of our reaction. In principle, any of
the multiple steps of the condensation reaction, or combina-
tions thereof, could govern the high selectivity. Even an
enantiomer differentiating interaction of the catalyst with the
amine enantiomers cannot be excluded at this point.
Mechanistic studies and an expansion of the scope of our
methodology are of high current interest in our laboratory.
resolutions of amines, see: (a) Paetzold, J.; Backvall, J. E. J. Am. Chem.
̈
Soc. 2005, 127, 17620. (b) Park, E.-S.; Malik, M. S.; Dong, J.-Y.; Shin,
J.-S. ChemCatChem 2013, 5, 1734. (c) Koszelewski, D.; Clay, D.;
Rozzell, D.; Kroutil, W. Eur. J. Org. Chem. 2009, 2009, 2289.
(6) For leading examples of small molecule catalyzed kinetic
resolutions of amines, see: (a) Arai, S.; Bellemin-Laponnaz, S.; Fu,
G. C. Angew. Chem., Int. Ed. 2001, 40, 234. (b) Arp, F. O.; Fu, G. C. J.
Am. Chem. Soc. 2006, 128, 14264. (c) Arnold, K.; Davies, B.; Herault,
D.; Whiting, A. Angew. Chem., Int. Ed. 2008, 47, 2673. (d) Hou, X. L.;
Zheng, B. H. Org. Lett. 2009, 11, 1789. (e) Reznichenko, A. L.;
Hampel, F.; Hultzsch, K. C. Chem. - Eur. J. 2009, 15, 12819. (f) De, C.
K.; Klauber, E. G.; Seidel, D. J. Am. Chem. Soc. 2009, 131, 17060.
(g) Klauber, E. G.; De, C. K.; Shah, T. K.; Seidel, D. J. Am. Chem. Soc.
2010, 132, 13624. (h) Klauber, E. G.; Mittal, N.; Shah, T. K.; Seidel,
D. Org. Lett. 2011, 13, 2464. (i) Binanzer, M.; Hsieh, S. Y.; Bode, J. W.
J. Am. Chem. Soc. 2011, 133, 19698. (j) Mittal, N.; Sun, D. X.; Seidel,
D. Org. Lett. 2012, 14, 3084. (k) Min, C.; Mittal, N.; De, C. K.; Seidel,
D. Chem. Commun. 2012, 48, 10853. (l) Hsieh, S.-Y.; Binanzer, M.;
Kreituss, I.; Bode, J. W. Chem. Commun. 2012, 48, 8892. (m) Allen, S.
E.; Hsieh, S.- Y.; Gutierrez, O.; Bode, J. W.; Kozlowski, M. C. J. Am.
Chem. Soc. 2014, 136, 11783. (n) Mittal, N.; Lippert, K. M.; De, C. K.;
Klauber, E. G.; Emge, T. J.; Schreiner, P. R.; Seidel, D. J. Am. Chem.
Soc. 2015, 137, 5748.
ASSOCIATED CONTENT
* Supporting Information
The Supporting Information is available free of charge on the
■
S
Experimental procedures, characterizations and analytical
data of products, and spectra of NMR and HPLC (PDF)
AUTHOR INFORMATION
Corresponding Author
(7) For small molecule catalyzed kinetic resolutions of derivatives of
amine, see: (a) Birman, V. B.; Jiang, H.; Li, X.; Guo, L.; Uffman, E. W.
J. Am. Chem. Soc. 2006, 128, 6536. (b) Fowler, B. S.; Mikochik, P. J.;
Miller, S. J. J. Am. Chem. Soc. 2010, 132, 2870. (c) Yang, X.; Bumbu, V.
D.; Birman, V. B. Org. Lett. 2011, 13, 4755. (d) Yang, X.; Bumbu, V.
D.; Liu, P.; Li, X.; Jiang, H.; Uffman, E. W.; Guo, L.; Zhang, W.; Jiang,
X.; Houk, K. N.; Birman, V. B. J. Am. Chem. Soc. 2012, 134, 17605.
(e) Xiao, K.-J.; Chu, L.; Chen, G.; Yu, J.-Q. J. Am. Chem. Soc. 2016,
138, 7796.
■
ORCID
Notes
The authors declare no competing financial interest.
(8) For noncatalytic kinetic resolutions of amines, see: (a) Krasnov,
V. P.; Gruzdev, D. A.; Levit, G. L. Eur. J. Org. Chem. 2012, 2012, 1471.
(b) Arseniyadis, S.; Valleix, A.; Wagner, A.; Mioskowski, C. Angew.
Chem., Int. Ed. 2004, 43, 3314. (c) Karnik, A. V.; Kamath, S. S.
Tetrahedron: Asymmetry 2008, 19, 45.
ACKNOWLEDGMENTS
■
Generous support by the Max-Planck-Society and the European
Research Council (Advanced Grant “CHAOS”) is gratefully
acknowledged. We thank the members of our NMR, MS,
HPLC, and X-ray crystallography departments for their
excellent service.
(10) For selected reviews on chiral phosphoric acid catalysis, see:
(a) Akiyama, T. Chem. Rev. 2007, 107, 5744. (b) Terada, M. Chem.
Commun. 2008, 44, 4097. (c) Hoffmann, S.; Seayad, A. M.; List, B.
Angew. Chem. 2005, 117, 7590. (d) Adair, G.; Mukherjee, S.; List, B.
Aldrichimica Acta 2008, 41, 31. (e) Terada, M. Synthesis 2010, 2010,
1929. (f) Kampen, D.; Reisinger, C. M.; List, B. Top. Curr. Chem.
2009, 291, 395. (g) Rueping, M.; Kuenkel, A.; Atodiresei, I. Chem. Soc.
Rev. 2011, 40, 4539.
(11) For examples of introducing bulky p-substituents into TRIP,
see: Cheng, X.; Goddard, R.; Buth, G.; List, B. Angew. Chem., Int. Ed.
2008, 47, 5079. (b) Cheon, C. H.; Yamamoto, H. J. Am. Chem. Soc.
2008, 130, 9246. (c) Horiguchi, K.; Yamamoto, E.; Saito, K.;
Yamanaka, M.; Akiyama, T. Chem. - Eur. J. 2016, 22, 8078.
(12) Under our optimized conditions, the unreacted free amine is
derivatized in situ with benzoic anhydride to ease isolation and
characterization. To isolate the free amine, the crude reaction mixture
is directly loaded onto a silica gel column, which is initially eluted with
30% Et2O−pentane (v/v) to obtain the enaminone product. Further
elution with 0.1:1:9 (triethylamine/methanol/ethyl acetate) then
provides the unreacted free amine.
REFERENCES
■
(1) (a) See for example: Schiff, H. Justus Liebigs Ann. Chem. 1864,
131, 118. (b) Kuhn, R.; Schretzmann, H. Chem. Ber. 1957, 90, 557.
(c) Stork, G.; Brizzolara, A.; Landesman, H.; Szmuszkovicz, J.; Terrell,
R. J. Am. Chem. Soc. 1963, 85, 207.
(2) See for example: (a) Kyte, J. Mechanism in Protein Chemistry, 1st
ed.; Garland Pub.: New York, 1995. (b) Mukherjee, S.; Yang, J. W.;
Hoffmann, S.; List, B. Chem. Rev. 2007, 107, 5471. (c) Erkkila, A.;
Majander, I.; Pihko, P. M. Chem. Rev. 2007, 107, 5416.
(3) (a) Kobayashi, S.; Ishitani, H. Chem. Rev. 1999, 99, 1069.
(b) Cordova, A. Acc. Chem. Res. 2004, 37, 102. (c) Petasis, N. A.;
́
Akritopoulou, I. Tetrahedron Lett. 1993, 34, 583. (d) Candeias, N. R.;
Montalbano, F.; Cal, P. M. S. D.; Gois, P. M. P. Chem. Rev. 2010, 110,
6169. (e) Strecker, A. Justus Liebigs Annalen der Chemie 1850, 75, 27.
(f) Wang, J.; Liu, X.; Feng, X. Chem. Rev. 2011, 111, 6947. (g) Pictet,
A.; Spengler, T. Ber. Dtsch. Chem. Ges. 1911, 44, 2030.
(h) Chrzanowska, M.; Rozwadowska, M. D. Chem. Rev. 2004, 104,
3341. (i) Knorr, L. Ber. Dtsch. Chem. Ges. 1884, 17, 2863. (j) Paal, C.
Ber. Dtsch. Chem. Ges. 1884, 17, 2756. (k) Rodionov, W. M. J. Am.
Chem. Soc. 1929, 51, 847. (l) Amarnath, V.; Anthony, D. C.;
Amarnath, K.; Valentine, W. M.; Wetterau, L. A.; Graham, D. G. J. Org.
Chem. 1991, 56, 6924. (m) Fields, E. K. J. Am. Chem. Soc. 1952, 74,
1528.
̈
(4) For selected examples of biocatalytic kinetic resolutions of
amines, see: (a) Turner, N. Nat. Chem. Biol. 2009, 5, 567. (b) Gotor-
Fernandez, V.; Gotor, V. Curr. Opin. Drug Discovery Dev. 2009, 12,
784. (c) Lee, J. H.; Han, K.; Kim, M.-J.; Park, J. Eur. J. Org. Chem.
2010, 2010, 999 and references cited therein.
C
J. Am. Chem. Soc. XXXX, XXX, XXX−XXX