Chemistry - A European Journal
10.1002/chem.202102394
FULL PAPER
Entry for the Table of Contents
Monomeric and dimeric organocatalysts behave differently.
Aldol and Michael reactions catalysed by dipeptides derived
from densely substituted unnatural proline derivatives show
different behaviours. In aldol reactions an additive scheme is
observed, whereas in conjugate reactions the catalytic activity of
these dipeptides constitutes an emergent property. Experimental,
kinetic and computational studies are reported to understand
these phenomena.
Institutional Twitter username: @upvehu
Researcher Twitter username: @CossioFp
[
1] a) Modern Methods in Stereoselective Aldol Reactions (Ed: R. Mahrwald),
Wiley-VCH Weinheim, 2011; b) B. M. Trost, C. S. Brindle, Chem. Soc. Rev.
010, 39, 1600–1632; c) Modern Aldol Reactions, Vols. 1 and 2 (Ed.: R.
Mahrwald), Wiley- VCH Weinheim, 2004.
2] J. L. Vicario, D. Badía, L. Carrillo, E. Reyes, Organocatalytic Conjugate
Addition Reactions; RSC Publishing Cambridge, U.K., 2010.
3] a) W. Notz, F. Tanaka, C. F. Barbas III, Acc. Chem. Res. 2004, 37, 580–591;
b) A. P. Brogan, T. J. Dickerson, K. D. Janda, Angew. Chem. Int. Ed. 2006, 45,
Biomol. Chem. 2011, 9, 6973–6978 ; c) S.-r. Ban, H.-y. Xie, X.-x. Zhu, Q.-s. Li,
Eur. J. Org. Chem. 2011, 6413–6417; d) S. Chandrasekhar, C. P. Kumar, T. P.
Kumar, K. Haribabu, B. Jagadeesh, J. K. Lakshmi, P. S. Mainkar, RSC Adv.
2014, 4, 30325–30331; e) A. Kamal, M. Sathish, V. Srinivasulu, J. Chetna, K.
C. Shekar, S. Nekkanti, Y. Tangella, N. Shankaraiah, Org. Biomol. Chem. 2014,
12, 8008–8018; f) C. K. Mahato, M. Kundu, A. Pramanik, Tetrahedron:
Asymmetry 2017, 28, 511–515; g) A. Castán, R. Badorrey, J. A. Galvez, P.
López-Ram-de-Víu, M. D. Diaz-de-Villegas, Org. Biomol. Chem. 2018, 16, 924–
935.
2
[
[
8
100–8102; c) S. Mukherjee, J. W. Yang, S. Hoffmann, B. List, Chem. Rev.
2007, 107, 5471–5569; d) A. Desmarchelier, V. Coeffard, X. Moreau, C. Greck,
[17] a) D. A. Alonso, A. Baeza, R. Chinchilla, C. Gómez, G. Guillena, I. M.
Tetrahedron 2014, 70, 2491–2513; e) N. Mase, Enamine Catalysis of Michael
Reactions, in Science of Synthesis, Asymmetric Organocatalysis 1: Lewis Base
and Acid Catalysis (Ed.: B. List), Georg Thieme Verlag Stuttgart, 2012, pp 135–
Pastor,
D.
J.
Ramón,
Molecules,
2017,
22,
895
(doi:
10.3390/molecules22060895); b) K. Patora-Komisarska, M. Benohoud, H.
Ishikawa, D. Seebach, Y. Hayashi, Helv. Chim. Acta 2011, 94, 719–745; c) D.
Seebach, X. Sun, C. Sparr, M.-O. Ebert, W. B. Schweizer, A. K. Beck, Helv.
Chim. Acta 2012, 95, 1064–1078; d) J. Bures, A. Armstrong, D. G. Blackmond,
J. Am. Chem. Soc. 2011, 133, 8822–8825; e) G. Sahoo, H. Rahaman, Á.
Madarász, I. Pápai, M. Melarto, A. Valkonen, P. M. Pihko, Angew. Chem. Int.
Ed. 2012, 51, 13144–13148.
236; f) J. Bures, A. Armstrong, D. G. Blackmond, D. G. Acc. Chem. Res. 2016,
49, 214–222.
[4] a) J .McMurry, T. Begley, The Organic Chemistry of Biological Pathways,
Roberts & Co. Englewood, Colorado, 2005; b) C.-I. Lin, R. M. McCarty, H.-W.
Liu, Angew. Chem. Int. Ed. 2017, 56, 3446–3489.
[
5] E. Lorentzen, B. Siebers, R. Hensel, E. Pohl, Biochemistry 2005, 44, 4222–
[18] a) M. Wiesner, J. D. Revell, H. Wennemers, Angew. Chem. Int. Ed. 2008,
47, 1871–1874; b) F. Bächle, J. Duschmalé, C. Ebner, A. Pfaltz, H. Wennemers,
Angew. Chem. Int. Ed. 2013, 52, 12619–12623; c) R. Kastl, H. Wennemers,
Angew. Chem. Int. Ed. 2013, 52, 7228–7232; d) Y. Arakawa, H. Wennemers,
ChemSucChem 2013, 6, 242–245; e) J. Duschmalé, J. Wiest, M. Wiesner, H.
Wennemers, Chem. Sci. 2013, 4, 1312–1318; f) J. Duschmalé, S. Kohrt, H.
Wennemers, Chem. Commun. 2014, 50, 8109–8112.
4
229.
[6] S. Raboni, S. Bettati, A. Mozzarelli, Cell. Mol. Life Sci. 2009, 66, 2391–2403.
[7] M. Baedeker, G. E. Schulz, Eur. J. Biochem. 2002, 269, 1790–1797.
[ 8 ] A. Berkessel, H. Gröger, Asymmetric Organocatalysis, Wiley-VCH
Weinheim, 2005; pp. 45–84, 314–322.
9] a) B. List, R. A. Lerner, C. F. Barbas III, J. Am. Chem. Soc. 2000, 122, 2395–
396; b) T. Bui, C. F. Barbas III, Tetrahedron Lett. 2000, 41, 6951–6954; c) C.
[
2
[19] A. Evidente, A. Andolfi, M. Vurro, M. C. Zonno, A. Motta, Phytochemistry
2000, 53, 231–237.
F. Barbas III, Angew. Chem. Int. Ed. 2008, 47, 42–47; d) B. List, P. Pojarliev, C.
Castello, Org. Lett. 2001, 3, 573–575; e) M. Agirre, A. Arrieta, I. Arrastia, F. P.
Cossío, Chem. Asian J. 2019, 14, 44–66.
[20] a) S. B. Tsogoeva, S. B. Jagtap, Z. A. Ardemasova, V. N. Kalikhevich, Eur.
J. Org. Chem. 2004, 4014–4019; b) S. B. Tsogoeva, S. B. Jagtap, Z. A.
Ardemasova, Tetrahedron: Asymmetry 2006, 17, 989–992.
[
10] a) K. A. Ahrendt, C. J. Borths, D. W. C. MacMillan, J. Am. Chem. Soc. 2000,
22, 4243–4244; b) D. W. C. MacMillan, Nature 2008, 455, 304–308.
11] a) E. A. C. Davie, S. M. Mennen, Y. Xu, S. J. Miller, Chem. Rev. 2007, 107,
759–5812; b) A. J. Metrano, S. J. Miller, Acc. Chem. Res. 2019, 52, 199–215.
12] K. Adamala, F. Anella, R. Wieczorek, P. Stano, C. Chiarabelli, P. L. Luisi,
Comput. Struct. Biotechnol. J. 2004, 9, e201402004.
13] a) C. Douat-Casassus, T. Darbre, J.-L. Reymond, J. Am. Chem. Soc.
004, 126, 7817–7826; b) E. Delort, T. Darbre, J.-L. Reymond, J. Am. Chem.
Soc. 2004, 126, 15642–15643.
14] a) S. B. Tsogoeva, S. B. Jagtap, Synlett 2004, 2624–2626; b) S. B.
Tsogoeva, S. Wei, Tetrahedron: Asymmetry 2005, 16, 1947–1951.
15] a) H. J. Martin, B. List, Synlett 2003, 1901–1902; b) J. Kofoed, J. Nielsen,
1
[21] I. Arrastia, A. Arrieta, F. P. Cossío, Eur. J. Org. Chem. 2018, 5889–5904.
[22] E. Conde, D. Bello, A. de Cózar, M. Sanchez, M. A. Vazquez, F. P. Cossío,
Chem. Sci. 2012, 3, 1486–1491.
[
5
[
[23] a) E. E. Maroto, S. Filippone, M. Suarez, R. Martinez-Álvarez, A. de Cózar,
F. P. Cossío, N. Martin, J. Am. Chem. Soc. 2014, 136, 705–712; b) E. Conde,
I. Rivilla, A. Larumbe, F. P. Cossío, J. Org. Chem. 2015, 80, 11755–11767.
[24] M. d. G. Retamosa, A. de Cozar, M. Sanchez, J. I. Miranda, J. M. Sansano,
L. M. Castello, C. Najera, A. I. Jimenez, F. J. Sayago, C. Cativiela, F. P. Cossio,
Eur. J. Org. Chem. 2015, 2503–2516.
[
2
[
[25] A. Sanchez-Sanchez, I. Rivilla, M. Agirre, A. Basterretxea, A. Etxeberria, A.
Veloso, H. Sardon, D. Mecerreyes, F. P. Cossio, J. Am. Chem. Soc. 2017, 139,
4805–4814.
[
J.-L. Reymond, Bioorg. Med. Chem. Lett. 2003, 13, 2445–2447; c) L.-X. Shi, Q.
Sun, Z.-M. Ge, Y.-Q. Zhu, T.-M. Cheng, R.-T.Li, Synlett, 2004, 2215–2217; d)
Z. Tang, Z.-H. Yang, L.-F. Cun, L.-Z. Gong, A.-Q. Mi, Y.-Z. Jiang, Org. Lett.
[26] A. Ruiz-Olalla, M. d. G. Retamosa, F. P. Cossio, J. Org. Chem. 2015, 80,
5588–5599.
2
004, 6, 2285–2287; e) Z. Tang, F. Jiang, X. Cu, L.-Z. Gong, A.-Q. Mi, Y.-Z.
[27] M. d. G. Retamosa, A. Ruiz-Olalla, T. Bello, A. de Cózar, F. P. Cossío,
Angew. Chem. Int. Ed. 2018, 57, 668–672.
Jiang, Y.-D. Wu, Proc. Natl. Ac. Sci. USA 2004, 101, 5755–5760; f) P. Krattiger,
R. Kovasy, J. D. Revell, S. Ivan, H. Wennemers, Org. Lett. 2005, 7, 1101–1103.
[28] a) P. L. Luisi, The emergence of life: from chemical origins to synthetic
chemistry, Cambridge University Press Cambridge, UK, 2016; b) A. Pross, What
[16] a) B. List, P. Pojarliev, H. J. Martin, Org. Lett. 2001, 3, 2423–2425; b) Z.
Zeng, P. Luo, Y. Jiang, Y. Liu, G. Tang, P. Xu, Y. Zhao, G. M. Blackburn, Org.
1
8
This article is protected by copyright. All rights reserved.