El renacer de un nuevo campo: la Organocatlisis Asimtrica.

Eugenia Marqus-Lpez y Raquel P. Herrera An. Qum. 2009, 105(1),

El desarrollo de nuevos procesos enantioselectivos constituye un campo de enorme

repercusin para la preparacin de compuestos enantiomricamente puros con
aplicaciones comerciales (productos farmacuticos, agroqumicos, piensos, fungicidas,
feromonas, esencias y aromas).

Por otra parte, en el caso de las reacciones llevadas a cabo en ausencia de metal,
podemos encontrar, en general, ventajas prcticas notables, tales como:

1.- No es necesario el uso de atmsfera inerte ni de disolventes anhidros.

2.- Las molculas orgnicas que se emplean como organocatalizadores son menos
costosas que los anlogos metlicos y ms estables que las enzimas y otros catalizadores
bioorgnicos.

3.- Estas molculas pueden ser inmovilizadas sobre un soporte slido y reutilizadas ms
fcilmente que los anlogos organometlicos/bioorgnicos.

Aunque los enlaces de hidrgeno representan una contribucin energtica de tan slo 1-
6 kcal/mol de las interacciones, influyen en la obtencin de una conformacin
preferente mediante la formacin de una estructura tridimensional rgida. De esta
manera contribuyen a la afinidad y selectividad en el reconocimiento molecular.
Tambin juegan un papel importante en la estabilizacin de los intermedios de reaccin
y modulando la reactividad de estos, de modo similar a la catlisis metlica.
 Hybrid-Type Squaramide-Fused Amino Alcohol
Organocatalysts for Enantioselective Nitro-Aldol Reaction
of Nitromethane with Isatins
Madhu Chennapuram, U. V. Subba Reddy, Chigusa Seki, Yuko Okuyama,
Eunsang Kwon, Koji Uwai, Michio Tokiwa Mitsuhiro Takeshita, and Hiroto
Nakano Eur. J. Org. Chem. 2017, 16381646

Small organic molecules as catalysts can provide complex organic transformations with
high levels of stereoselectivity in an environmentally and economically friendly manner.

In recent years, we have explored simple primary amino alcohols as a new class of
organocatalyst with distinctive features such as ease of synthesis, stability upon
exposure to air, potential towards steric-site modifications, and capability as a
bifunctional (enamine activation and noncovalent activation) catalyst.

In continuation of our efforts towards expanding the scope of amino alcohols and their
derivatives as organocatalysts, we herein focused on the synthesis of squaramide-fused
amino alcohols A and B (Scheme 3), which have multiple hydrogen- bonding and
stereoinduction sites within the same molecule, and evaluated their catalytic activity in
the nitro-aldol reaction of isatins with nitroalkanes. These simple amino alcohols that
contain covalent and noncovalent hydrogen-bonding sites within the same molecule
work as efficient organocatalysts in many enantioselective reactions
 Organocatalysts for enantioselective
synthesis of fine chemicals: definitions,
trends and developments
Chiara Palumbo* and Matteo Guidotti

The word Organocatalysis has been introduced in the scientific community in 2000 by
MacMillan, one of the pioneers of the field. Organocatalysis refers to the use of small
organic molecules to catalyze organic transformations.

In the former case, within the catalytic cycle, the catalyst covalently binds the substrate,
in the latter case only non-covalent interactions, such as hydrogen bonding or the
formation of ion pairs, activate the molecule towards the asymmetric transformation.

They clearly resemble the enzymatic pockets found in serine proteases for the activation
of the amide carbonyl towards the serine nucleophilic attack. Within what is called the
oxyanion hole, the amide carbonyl is coordinated and activated by two NH groups,
hence favouring the serine nucleophilic attack with the formation of a tetrahedral
intermediate stabilized by H-bonding.

En lo que denominamos agujero oxianinico el carbonilo de la amida es coordinado y

activado por dos grupos NH, lo que facilita el ataque nucleoflico de la serina y la
formacin de un intermedio tetradrico que queda estabilizado por enlace de hodrgeno.
 Silyloxy Amino Alcohol Organocatalyst for Enantioselective
1,3-Dipolar Cycloaddition of Nitrones to a,-Unsaturated
Aldehydes

T. Otsuki, Y. Kohari, Y. Okuyama, E. Kwon, C. Seki, K. Uwai, Y. Mawatari, N. Kobayashi, T. Iwasa, M.

Tokiwa, M. Takeshita, A. Maeda, A. Hashimoto, K. Turuga, and H. Nakano; Eur. J. Org. Chem. 2015,
72927300

Y. Kohari, Y. Okuyama, E. Kwon, T. Furuyama, N. Kobayashi, T. Otuki, J. Kumagai, C. Seki, K. Uwai, G. Dai, T.
Iwasa, H. Nakano, J. Org. Chem. 2014, 79, 9500;

Recently, we reported that an amino alcohol that contains a primary amino group can
act as an efficient organocatalyst in the enantioselective DielsAlder reaction of 1,2-
dihydropyridines with dienophiles. In summary, new catalytically active amino alcohol
or-ganocatalysts which contain a primary amine, worked effectively as organocatalysts.