Stereochemical editing has recently risen to prominence, allowing the direct editing of organic molecules with stereocenter(s) to adjust their relative stereochemistry at a late-stage. Several seminal light-driven stereochemical editing reactions such as deracemization and epimerization have been successively developed. Recently, Wendlandt and co-workers reported a versatile photochemical epimerization of unactivated tertiary stereogenic centers to rapidly prepare the stereoisomers that were previously challenging to access.
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http://dx.doi.org/10.1002/anie.202217840 | DOI Listing |
Nat Chem
January 2025
Shenzhen Grubbs Institute, Department of Chemistry, Southern University of Science and Technology, Shenzhen, China.
The substitution of an aromatic ring with a C(sp)-rich bicyclic hydrocarbon, known as bioisosteric replacement, plays a crucial role in modern drug discovery. Substituted bicyclo[1.1.
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August 2024
State Key Laboratory of Coordination Chemistry, Chemistry and Biomedicine Innovation Center (ChemBIC), School of Chemistry and Chemical Engineering, Nanjing University, Nanjing, Jiangsu, China.
Recent strides in C-H borylation have significantly expanded our toolkit for the preparation of organoboronates. Nevertheless, avenues alternative to obtain these compounds via σ-C-C cleavage, thereby facilitating molecular scaffold editing, remain scarce. Several methodologies have been proposed for hydroboration of cyclopropanes by activating C-C bonds, conventionally relying on noble and hazardous metal catalysts to control reaction outcomes.
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July 2024
Department of Chemistry, Massachusetts Institute of Technology, Cambridge, MA 02139, USA.
Stereochemical editing strategies have recently enabled the transformation of readily accessible substrates into rare and valuable products. Typically, site selectivity is achieved by minimizing kinetic complexity by using protecting groups to suppress reactivity at undesired sites (substrate control) or by using catalysts with tailored shapes to drive reactivity at the desired site (catalyst control). We propose "network control," a contrasting paradigm that exploits hidden interactions between rate constants to greatly amplify modest intrinsic biases and enable precise multisite editing.
View Article and Find Full Text PDFOrg Lett
June 2024
Department of Chemistry, Yale University, New Haven, Connecticut 04720, United States.
Angew Chem Int Ed Engl
November 2023
Department Chemie and Catalysis Research Center (CRC), School of Natural Sciences, Technische Universität München, D-85747, Garching, Germany.
2,5-Diketopiperazines are cyclic dipeptides displaying a wide range of applications. Their enantioselective preparation has now been found possible from the respective racemates by a photochemical deracemization (53 examples, 74 % to quantitative yield, 71-99 % ee). A chiral benzophenone catalyst in concert with irradiation at λ=366 nm enables to establish the configuration at the stereogenic carbon atom C6 at will.
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