Organocatalysis by Hydrogen Bonding Networks
295
the azlactone/oxazinone opening involve a naturally evolved catalytic
principle. It is tempting to speculate which other types of enzymatic
rate acceleration by hydrogen bonding might be suitable for adaptation to organocatalysis. Along the same lines, one may wonder whether
organocatalysts might eventually substitute for enzymes—potentially in
a living cell.
Acknowledgements. This work was supported financially by the EU (Research
Training Networks ‘The Discovery of New Molecular Catalysts through Combinatorial Chemistry: Activity and Selectivity from Diversity’, COMBICAT,
RTN-CT-2000–00014 and ‘(R)Evolutionary Catalysis’, REVCAT, MRTN-CT2006–038566), the Deutsche Forschungsgemeinschaft (Priority Program
‘Organocatalysis’, SPP 1179), the Fonds der Chemischen Industrie, and by the
BASF AG, Ludwigshafen. Generous gifts of amino acids by the Degussa AG,
Hanau, are gratefully acknowledged.
References
Berkessel A, Adrio JA (2004) Kinetic studies of olefin epoxidation with hydrogen peroxide in 1,1,1,3,3,3-hexafluoro-2-propanol reveal a crucial catalytic
role for solvent clusters. Adv Synth Catal 346:275–280
Berkessel A, Adrio JA (2006) Dramatic acceleration of olefin epoxidation in
fluorinated alcohols: activation of hydrogen peroxide by multiple H-bond
networks. J Am Chem Soc 128:13412–13420
Berkessel A, Adrio JA, Hüttenhain D, Neudörfl JM (2006a) Unveiling the
“booster effect” of fluorinated alcohol solvents: aggregation-induced conformational changes, and cooperatively enhanced H-bonding. J Am Chem
Soc 128:8421–8426
Berkessel A, Andreae MRM (2001) Efficient catalytic methods for the BaeyerVilliger oxidation and epoxidation with hydrogen peroxide. Tetrahedron
Lett 42:2293–2295
Berkessel A, Andreae MRM, Schmickler H, Lex J (2002) Baeyer–Villiger oxidations with hydrogen peroxide in fluorinated alcohols: lactone formation
by a nonclassical mechanism. Angew Chem Int Ed 41:4481–4484
Berkessel A, Cleemann F, Mukherjee S (2005a) Kinetic resolution of oxazinones: an organocatalytic approach to enantiomerically pure beta-amino
acids. Angew Chem Int Ed 44:7466–7469
Berkessel A, Cleemann F, Mukherjee S, Müller TN, Lex J (2005b) Highly efficient dynamic kinetic resolution of azlactones by urea-based bifunctional
organocatalysts. Angew Chem Int Ed 44:807–811
295
the azlactone/oxazinone opening involve a naturally evolved catalytic
principle. It is tempting to speculate which other types of enzymatic
rate acceleration by hydrogen bonding might be suitable for adaptation to organocatalysis. Along the same lines, one may wonder whether
organocatalysts might eventually substitute for enzymes—potentially in
a living cell.
Acknowledgements. This work was supported financially by the EU (Research
Training Networks ‘The Discovery of New Molecular Catalysts through Combinatorial Chemistry: Activity and Selectivity from Diversity’, COMBICAT,
RTN-CT-2000–00014 and ‘(R)Evolutionary Catalysis’, REVCAT, MRTN-CT2006–038566), the Deutsche Forschungsgemeinschaft (Priority Program
‘Organocatalysis’, SPP 1179), the Fonds der Chemischen Industrie, and by the
BASF AG, Ludwigshafen. Generous gifts of amino acids by the Degussa AG,
Hanau, are gratefully acknowledged.
References
Berkessel A, Adrio JA (2004) Kinetic studies of olefin epoxidation with hydrogen peroxide in 1,1,1,3,3,3-hexafluoro-2-propanol reveal a crucial catalytic
role for solvent clusters. Adv Synth Catal 346:275–280
Berkessel A, Adrio JA (2006) Dramatic acceleration of olefin epoxidation in
fluorinated alcohols: activation of hydrogen peroxide by multiple H-bond
networks. J Am Chem Soc 128:13412–13420
Berkessel A, Adrio JA, Hüttenhain D, Neudörfl JM (2006a) Unveiling the
“booster effect” of fluorinated alcohol solvents: aggregation-induced conformational changes, and cooperatively enhanced H-bonding. J Am Chem
Soc 128:8421–8426
Berkessel A, Andreae MRM (2001) Efficient catalytic methods for the BaeyerVilliger oxidation and epoxidation with hydrogen peroxide. Tetrahedron
Lett 42:2293–2295
Berkessel A, Andreae MRM, Schmickler H, Lex J (2002) Baeyer–Villiger oxidations with hydrogen peroxide in fluorinated alcohols: lactone formation
by a nonclassical mechanism. Angew Chem Int Ed 41:4481–4484
Berkessel A, Cleemann F, Mukherjee S (2005a) Kinetic resolution of oxazinones: an organocatalytic approach to enantiomerically pure beta-amino
acids. Angew Chem Int Ed 44:7466–7469
Berkessel A, Cleemann F, Mukherjee S, Müller TN, Lex J (2005b) Highly efficient dynamic kinetic resolution of azlactones by urea-based bifunctional
organocatalysts. Angew Chem Int Ed 44:807–811