ChemInform Abstract: Enantioselective Organocatalysis

Gaunt, Matthew J.; Johansson, Carin C. C.; McNally, Andy; Vo, Ngoc T.

doi:10.1002/chin.200803246

Cited by 2 publications

(4 citation statements)

References 1 publication

Supporting

Mentioning

Contrasting

Order By: Relevance

“…4 Organocatalysts demonstrated wide applicability due to their nontoxic nature, availability, stability and recyclability compared to conventional metal catalysts. 5,6 Cinchona alkaloids (CA), natural compounds and wellknown members of the organocatalyst family, are extensively used for chiral molecular recognition and enantioselective catalysis (Scheme 1). 7 CA and their derivatives are highly effective in catalytic asymmetric reactions due to their structural diversity and conformational flexibility.…”

Section: Introductionmentioning

confidence: 99%

“…7 CA and their derivatives are highly effective in catalytic asymmetric reactions due to their structural diversity and conformational flexibility. 6,7 Design, application, and choice of CA play a prominent role in the catalysis of specific reactions, yielding excellent stereoselectivities with enhanced catalytic efficiency. In 1912, Bredig and Fiske reported the first asymmetric reaction using cinchona alkaloids.…”

Section: Introductionmentioning

confidence: 99%

See 1 more Smart Citation

Computational Studies on Cinchona Alkaloid-Catalyzed Asymmetric Organic Reactions

et al. 2016

View full text Add to dashboard Cite

Remarkable progress in the area of asymmetric organocatalysis has been achieved in the last decades. Cinchona alkaloids and their derivatives have emerged as powerful organocatalysts owing to their reactivities leading to high enantioselectivities. The widespread usage of cinchona alkaloids has been attributed to their nontoxicity, ease of use, stability, cost effectiveness, recyclability, and practical utilization in industry. The presence of tunable functional groups enables cinchona alkaloids to catalyze a broad range of reactions. Excellent experimental studies have extensively contributed to this field, and highly selective reactions were catalyzed by cinchona alkaloids and their derivatives. Computational modeling has helped elucidate the mechanistic aspects of cinchona alkaloid catalyzed reactions as well as the origins of the selectivity they induce. These studies have complemented experimental work for the design of more efficient catalysts. This Account presents recent computational studies on cinchona alkaloid catalyzed organic reactions and the theoretical rationalizations behind their effectiveness and ability to induce selectivity. Valuable efforts to investigate the mechanisms of reactions catalyzed by cinchona alkaloids and the key aspects of the catalytic activity of cinchona alkaloids in reactions ranging from pharmaceutical to industrial applications are summarized. Quantum mechanics, particularly density functional theory (DFT), and molecular mechanics, including ONIOM, were used to rationalize experimental findings by providing mechanistic insights into reaction mechanisms. B3LYP with modest basis sets has been used in most of the studies; nonetheless, the energetics have been corrected with higher basis sets as well as functionals parametrized to include dispersion M05-2X, M06-2X, and M06-L and functionals with dispersion corrections. Since cinchona alkaloids catalyze reactions by forming complexes with substrates via hydrogen bonds and long-range interactions, the use of split valence triple-ζ basis sets including diffuse and polarization functions on heavy atoms and polarization functions on hydrogens are recommended. Most of the studies have used the continuum-based models to mimic the condensed phase in which organocatalysts function; in some cases, explicit solvation was shown to yield better quantitative agreement with experimental findings. The conformational behavior of cinchona alkaloids is also highlighted as it is expected to shed light on the origin of selectivity and pave the way to a comprehensive understanding of the catalytic mechanism. The ultimate goal of this Account is to provide an up-to-date overlook on cinchona alkaloid catalyzed chemistry and provide insight for future studies in both experimental and theoretical fields.

show abstract

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Computational Studies on Cinchona Alkaloid-Catalyzed Asymmetric Organic Reactions

et al. 2016

View full text Add to dashboard Cite

show abstract

“…Aminocatalysts Since List, Lerner, and Barbas 374 established the use of L-proline to promote the enantioselective direct Aldol reaction between unmodified ketones and aldehydes, chiral cyclic secondary amines have been widely used to catalyze the asymmetric functionalization of carbonyl compounds. 20,24,25,374 Aminocatalysis via enamine and iminium ion intermediates has now emerged as a powerful strategy for the synthesis of a plethora of optically active organic compounds as new transformations are continuously being discovered, and new catalysts are being designed and applied in asymmetric synthesis. 375−377 In particular, aminocatalysis through enamine activation of the highest occupied molecular orbital (HOMO) rising appeared as a major contributor in the area of organocatalysis and has been applied in several asymmetric transformations/cascade reactions.…”

Section: Covalent Catalysismentioning

confidence: 99%

“…In 2013, our research group 413 developed mild routes to novel carbapenem β-ketoester derivatives through C−C bond-forming reactions using L-proline 20,24 as an efficient organocatalyst. The carbapenem core is a class of β-lactam antibiotics that have been recognized as one of the most powerful and broad-spectrum antibiotics in clinical use.…”

Section: Covalent Catalysismentioning

confidence: 99%

Enantioselective Organocatalyzed Transformations of β-Ketoesters

et al. 2016

View full text Add to dashboard Cite

The β-ketoester structural motif continues to intrigue chemists with its electrophilic and nucleophilic sites. Proven to be a valuable tool within organic synthesis, natural product, and medicinal chemistry, reports on chiral β-ketoester molecular skeletons display a steady increase. With the reignition of organocatalysis in the past decade, asymmetric methods available for the synthesis of this structural unit has significantly expanded, making it one of the most exploited substrates for organocatalytic transformations. This review provides comprehensive information on the plethora of organocatalysts used in stereoselective organocatalyzed construction of β-ketoester-containing compounds.

show abstract

ChemInform Abstract: Enantioselective Organocatalysis

Cited by 2 publications

References 1 publication

Computational Studies on Cinchona Alkaloid-Catalyzed Asymmetric Organic Reactions

Computational Studies on Cinchona Alkaloid-Catalyzed Asymmetric Organic Reactions

Enantioselective Organocatalyzed Transformations of β-Ketoesters

Contact Info

Product

Resources

About