Chiral phosphoric acid catalysis: from numbers to insights

2018 ◽  
Vol 47 (4) ◽  
pp. 1142-1158 ◽  
Author(s):  
Rajat Maji ◽  
Sharath Chandra Mallojjala ◽  
Steven E. Wheeler
Keyword(s):  
Phosphoric Acid ◽  
Quantum Chemistry ◽  
Acid Catalysis ◽  
Asymmetric Reactions ◽  
Computational Quantum Chemistry ◽  
Chiral Phosphoric Acid ◽  
Computational Quantum ◽  
Phosphoric Acids

Chiral phosphoric acids (CPAs) have emerged as powerful organocatalysts for asymmetric reactions, and applications of computational quantum chemistry have revealed important insights into the activity and selectivity of these catalysts.

Secondary stereocontrolling interactions in chiral Brønsted acid catalysis: study of a Petasis–Ferrier-type rearrangement catalyzed by chiral phosphoric acids

2014 ◽  
Vol 5 (9) ◽  
pp. 3515-3523 ◽  
Author(s):  
Kyohei Kanomata ◽  
Yasunori Toda ◽  
Yukihiro Shibata ◽  
Masahiro Yamanaka ◽  
Seiji Tsuzuki ◽  
...  
Keyword(s):  
Hydrogen Bonds ◽  
Phosphoric Acid ◽  
Acid Catalysis ◽  
Computational Studies ◽  
Stacking Interactions ◽  
Π Stacking ◽  
Chiral Phosphoric Acid ◽  
Acid Catalyzed ◽  
Chiral Bronsted Acid ◽  
Phosphoric Acids

Guided by computational studies, the involvement of non-classical C–H⋯O hydrogen bonds and π–π stacking interactions were found to be crucial for high stereocontrol in a chiral phosphoric acid-catalyzed reaction.

Enantioselective synthesis of cyclic quaternary α-amino acid derivatives by chiral phosphoric acid catalysis

2017 ◽  
Vol 15 (28) ◽  
pp. 6033-6041 ◽  
Author(s):  
Lei Wang ◽  
Abdul Rahman ◽  
Xufeng Lin
Keyword(s):  
Amino Acid ◽  
Phosphoric Acid ◽  
Acid Catalysis ◽  
Enantioselective Synthesis ◽  
Amino Acid Derivatives ◽  
Chiral Phosphoric Acid ◽  
Efficient Route ◽  
Quaternary Stereocenter ◽  
High Yields ◽  
Phosphoric Acids

Development of highly enantioselective aza-Friedel–Crafts reaction of N-sulfonyl cyclic ketimines with indoles catalyzed by chiral phosphoric acids, providing an efficient route to indole-containing chiral cyclic α-amino acid derivatives bearing quaternary stereocenter in high yields and up to 98% enantioselectivity.

Chiral Phosphoric Acid Catalyzed Regio- and Enantioselective Reactions of Functionalized Propargylic Alcohols

2022 ◽  
Author(s):  
Chenxiao Qian ◽  
Meiwen Liu ◽  
Jianwei Sun ◽  
Pengfei Li
Keyword(s):  
Phosphoric Acid ◽  
Asymmetric Reactions ◽  
Propargylic Alcohols ◽  
Chiral Phosphoric Acid ◽  
Wide Range ◽  
Enantioselective Reactions ◽  
Acid Catalyzed ◽  
Catalyzed Reactions ◽  
Phosphoric Acids

Propargylic alcohols have been known as useful substrates in a wide range of asymmetric reactions. Particularly, the chiral phosphoric acids (CPAs) catalyzed reactions of functionalized propargylic alcohols opened a robust...

Computational predictions of metal-macrocycle stability constants require accurate treatments of local solvent and pH effects

2021 ◽  
Author(s):  
Brian Gentry ◽  
Tae Hoon Choi ◽  
William S. Belfield ◽  
John A. Keith
Keyword(s):  
Quantum Chemistry ◽  
Rational Design ◽  
Chelating Agents ◽  
Ph Effects ◽  
Detailed Understanding ◽  
Metal Interactions ◽  
Solvent Phase ◽  
Computational Quantum Chemistry ◽  
Computational Predictions ◽  
Computational Quantum

Rational design of molecular chelating agents requires a detailed understanding of physicochemical ligand-metal interactions in solvent phase. Computational quantum chemistry methods should be able to provide this, but computational reports...

scholarly journals Rayleigh-Ritz Majorization Error Bounds for the Linear Response Eigenvalue Problem

2019 ◽  
Vol 17 (1) ◽  
pp. 653-667
Author(s):  
Zhongming Teng ◽  
Hong-Xiu Zhong
Keyword(s):  
Eigenvalue Problem ◽  
Quantum Chemistry ◽  
Error Bounds ◽  
Linear Response ◽  
Computational Quantum Chemistry ◽  
Matrix Anal ◽  
Deflating Subspaces ◽  
Important Notion ◽  
Theoretical Foundations ◽  
Computational Quantum

Abstract In the linear response eigenvalue problem arising from computational quantum chemistry and physics, one needs to compute a few of smallest positive eigenvalues together with the corresponding eigenvectors. For such a task, most of efficient algorithms are based on an important notion that is the so-called pair of deflating subspaces. If a pair of deflating subspaces is at hand, the computed approximated eigenvalues are partial eigenvalues of the linear response eigenvalue problem. In the case the pair of deflating subspaces is not available, only approximate one, in a recent paper [SIAM J. Matrix Anal. Appl., 35(2), pp.765-782, 2014], Zhang, Xue and Li obtained the relationships between the accuracy in eigenvalue approximations and the distances from the exact deflating subspaces to their approximate ones. In this paper, we establish majorization type results for these relationships. From our majorization results, various bounds are readily available to estimate how accurate the approximate eigenvalues based on information on the approximate accuracy of a pair of approximate deflating subspaces. These results will provide theoretical foundations for assessing the relative performance of certain iterative methods in the linear response eigenvalue problem.

Asymmetric C-H and N-H functionalization of Indoles involving Central Chirality via Chiral Phosphoric Acid Catalysis

2021 ◽  
Vol 18 ◽  
Author(s):  
Alemayehu Gashaw ◽  
Dereje Kebebew Debeli ◽  
Meseret Chemeda
Keyword(s):  
Phosphoric Acid ◽  
Organic Compounds ◽  
Organic Synthesis ◽  
Acid Catalysis ◽  
Bond Formation ◽  
Acid Catalysts ◽  
Asymmetric Syntheses ◽  
Chiral Phosphoric Acid ◽  
Great Progress ◽  
Interesting Area

: The C-H and N-H functionalization of indoles is an interesting area of research that has a useful impact on organic synthesis due to the availability of chiral indole scaffolds in the discovery of drugs, synthetic bioactive compounds, and natural products. The chiral phosphoric acid catalysts (CPAs) have proven to be a powerful and versatile class of enantioselective organocatalysts. Many asymmetric syntheses of organic compounds have been carried out with these catalysts in C–C and C-N bond formation reactions, and great progress has been reported. By 2011, several reviews were published covering some important topics and recent achievements in this field. Therefore, in this review, the most recent advances, research breakthroughs with key examples involving mechanisms of CPA-catalyzed C-H and N-H functionalization of indoles to form central chirality via Friedel Crafts, Michael type, and rearrangement reactions were reviewed and reported.

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