Article
Chemistry, Physical
Chunhui Zhang, Jijun Jiang, Xiaoyu Huang, Jun Wang
Summary: A new type of CpRh(III) catalyst has been successfully designed and synthesized for asymmetric C-H activation. The catalyst, with prochiral tetrasubstituted Cp-px ligands, showed high catalytic activity in various reactions, achieving high yields and enantiomeric excesses.
Review
Chemistry, Multidisciplinary
Oleksandr Vyhivskyi, Anton Kudashev, Takeru Miyakoshi, Olivier Baudoin
Summary: Processes involving transition-metal catalysis have become a major part of synthetic chemists' toolbox in recent decades. The focus has shifted from cross-coupling reactions to C-H bond functionalization, with constant progress leading to discovery of enantioselective methods. The review discusses enantioselective Pd-0-catalyzed C-H activation, highlighting the importance of different chiral ligands and catalysts in enabling these transformations.
CHEMISTRY-A EUROPEAN JOURNAL
(2021)
Article
Chemistry, Physical
Hui Yang, Ru Zhang, Su-Zhen Zhang, Qing Gu, Shu-Li You
Summary: Researchers have developed a series of chiral spiro ligands (BCSCp) from commercially available and cheap Bisphenol C, and prepared their corresponding rhodium complexes. These complexes have been successfully applied in enantioselective aryl C-H addition to nitroalkenes, producing C-H adducts with yields up to 88% and ee up to 98%.
Article
Chemistry, Physical
Tatsuhiko Yoshino, Shigeki Matsunaga
Summary: Enantioselective C-H functionalization is a powerful tool for synthesizing chiral molecules. The combination of high-valent group 9 metals with achiral Cp-x ligands and chiral carboxylic acids has shown promise in enabling selective cleavage and functionalization of enantiotopic C-H bonds. This Perspective provides a detailed summary of the background, catalyst design, applied reactions, and future directions in this field.
Article
Chemistry, Physical
Yoshimi Kato, Luqing Lin, Masahiro Kojima, Tatsuhiko Yoshino, Shigeki Matsunaga
Summary: By introducing pseudo-C2 symmetric tunable chiral carboxylic acids, the study achieved enantioselective C(sp(3))-H amidation reactions of substrates such as 2-alkylpyridines, improving the chiral selectivity towards the substrates.
Review
Chemistry, Multidisciplinary
Josep Mas-Rosello, Ana G. Herraiz, Benoit Audic, Aragorn Laverny, Nicolai Cramer
Summary: The development of new chiral ligands is crucial for stereocontrol in metal-catalyzed reactions, especially with the increasing demand for bioactive molecules as single enantiomers. The successful application of Cp-X ligands in metal-catalyzed transformations allows access to valuable chiral molecules, with critical comparisons of existing ligand families and discussion of future research directions for further enhancing their performance and application in enantioselective catalysis.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2021)
Article
Chemistry, Inorganic & Nuclear
Andrey V. Kolos, Yulia V. Nelyubina, Evgeniya S. Podyacheva, Dmitry S. Perekalin
Summary: The rhodium complexes with asymmetric cyclopentadienyl ligands were prepared and demonstrated good catalytic activity for the reactions of arylhydroxamates with alkenes. Although the enantioselectivity of the reaction was moderate, the yields were excellent.
DALTON TRANSACTIONS
(2023)
Review
Chemistry, Multidisciplinary
David Laws III, Christopher D. Poff, Ethan M. Heyboer, Simon B. Blakey
Summary: Planar chirality is an important form of molecular chirality that can induce enantioselectivity in transition metal catalysts. However, there are limitations in using late transition metal planar chiral complexes for enantioselective transformations due to synthetic constraints. Additionally, the methods for stereochemical assignment of planar chiral compounds are sometimes conflicting. This review aims to provide clarity on the assignment methods and overview the synthesis and use of late transition metal planar chiral complexes as enantioselective catalysts.
CHEMICAL SOCIETY REVIEWS
(2023)
Article
Chemistry, Organic
Takeshi Yasui, Shouta Tanabe, Takuya Masueda, Yoshihiko Yamamoto
Summary: Here, a concise method for preparing functionalized cyclopentadienyl rhodium complexes via Suzuki-Miyaura cross-coupling is reported. The conversion of 2,3,4,5-tetramethylcyclopent-2-en-1-one into the cyclopentadienylboronic acid pinacol ester, which serves as a coupling partner with aryl halides, was successfully achieved. Various functionalized cyclopentadienyl rhodium complexes were synthesized from commercially available aryl bromides in two steps. Additionally, a novel chiral cyclopentadienyl rhodium complex was rapidly synthesized as a precatalyst for an asymmetric C-H functionalization reaction.
SYNTHESIS-STUTTGART
(2023)
Article
Chemistry, Organic
Yang An, Xiao-Yan Zhang, Ya-Nan Ding, Yuke Li, Xue-Yuan Liu, Yong-Min Liang
Summary: This study synthesized ferrocenes with planar chirality using palladium/chiral norbornene cooperative catalysis and axial-to-planar diastereoinduction. The chiral norbornene was used to control the aromatic axial chirality and induce the planar chirality of ferrocene through C(sp2)-H activation.
Article
Chemistry, Organic
Zengyin Chao, Na Li, Biqiong Hong, Mingming Ma, Zhenhua Gu
Summary: A palladium-catalyzed ring-opening reaction of optically active ferrocenyl tertiary alcohols for the construction of planar chiral ketones was reported. The stereochemistry of the hydroxyl group in ferrocenyl alcohols significantly affects the reaction, with beta-hydroxyl group showing better reactivity and chemoselectivity. Treatment of alpha-hydroxyl substrates with trifluoroacetic acid successfully enables the inversion of the hydroxyl group orientation to the corresponding beta-analogues.
Article
Chemistry, Multidisciplinary
Ziyang Dong, Jia Li, Ting Yao, Changgui Zhao
Summary: Planar-chiral cyclophanes have attracted increasing attention in drug discovery and catalyst design. This paper describes the first Pd(II)-catalyzed enantioselective C-H olefination of prochiral cyclophanes. The reaction proceeds through dynamic kinetic resolution, providing high yields and excellent enantioselectivities.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Multidisciplinary
Matthias Peeters, Jonathan Decaens, Alois Fuerstner
Summary: Chiral [BiRh]-paddlewheel complexes empowered by London dispersion enable the generation of (trifluoromethyl)furfurylidene metal complexes from a bench-stable triftosylhydrazone precursor. These complexes undergo asymmetric [2+1] cycloadditions, providing optically active trifluoromethylated cyclopropane or -cyclopropene derivatives, which are important building blocks for medicinal chemistry and difficult to obtain in optically active form.
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION
(2023)
Article
Chemistry, Inorganic & Nuclear
Kristina Zivkovic, Lilia M. Baldauf, Jessica L. Cryder, Alexa Villasenor, Valeria Reyes, Lauren E. Bernier, Theresa J. Thomas, Maxwell O'Toole, Kayleen Fulton, Curtis E. Moore, Arnold L. Rheingold, Christopher J. A. Daley
Summary: The study reports the first isolation and structural characterization of a series of chiral trinitrogen pincer ligands, as well as the methods for their preparation. Experimental results show that a novel microwave-based technique is more efficient, although currently not scalable.
DALTON TRANSACTIONS
(2021)
Article
Chemistry, Multidisciplinary
Nikita M. Ankudinov, Yulia Nelyubina, Dmitry S. Perekalin
Summary: Diene rhodium complexes with uncommon planar chirality were successfully synthesized through face-selective coordination, resulting in high yields and exceptional diastereoselectivity. The subsequent replacement of the auxiliary ligand retained the planar chirality.
CHEMISTRY-A EUROPEAN JOURNAL
(2022)
