Matteson homologation, a successive extension of chiral boronic esters, is perfectly suited for the synthesis of complex molecular structures containing several stereogenic centers. The "classical version" allows the introduction of various functional groups in a 1,2--configuration. The absolute configuration is determined by the choice of the chiral auxiliary, which can be used to introduce several stereogenic centers. In contrast, in Aggarwal's lithiation-borylation strategy, new chiral auxiliary reagents must be used in each reaction step, which on the other hand allows the individual insertion of the desired stereogenic centers. Both methods have their individual advantages and disadvantages and are well suited for the synthesis of marine natural products.
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http://dx.doi.org/10.3390/md23010020 | DOI Listing |
Chem Commun (Camb)
January 2025
State Key Laboratory of Green Pesticide, Fine Chemical Research and Development Center, Guizhou University, Huaxi District, Guiyang 550025, China.
Herein, we developed a practical approach using stable, cost-effective ammonium salts with an organic base to generate anhydrous ammonia for asymmetric sulfinylation, achieving a broad range of enantioenriched sulfinamides with excellent yields and optical purity. Additionally, these sulfinamide products serve as versatile precursors for S-stereogenic functional molecules with potential in organic synthesis and drug discovery.
View Article and Find Full Text PDFMar Drugs
January 2025
Organic Chemistry, Saarland University, Campus Building C4.2, D-66123 Saarbruecken, Germany.
Matteson homologation, a successive extension of chiral boronic esters, is perfectly suited for the synthesis of complex molecular structures containing several stereogenic centers. The "classical version" allows the introduction of various functional groups in a 1,2--configuration. The absolute configuration is determined by the choice of the chiral auxiliary, which can be used to introduce several stereogenic centers.
View Article and Find Full Text PDFAcc Chem Res
January 2025
Shenzhen Grubbs Institute and Department of Chemistry, Shenzhen Key Laboratory of Small Molecule Drug Discovery and Synthesis, Guangdong Provincial Key Laboratory of Catalysis, Southern University of Science and Technology, Shenzhen, Guangdong 518055, China.
ConspectusChiral organosilicon compounds bearing a Si-stereogenic center have attracted increasing attention in various scientific communities and appear to be a topic of high current relevance in modern organic chemistry, given their versatile utility as chiral building blocks, chiral reagents, chiral auxiliaries, and chiral catalysts. Historically, access to these non-natural Si-stereogenic silanes mainly relies on resolution, whereas their asymmetric synthetic methods dramatically lagged compared to their carbon counterparts. Over the past two decades, transition-metal-catalyzed desymmetrization of prochiral organosilanes has emerged as an effective tool for the synthesis of enantioenriched Si-stereogenic silanes.
View Article and Find Full Text PDFChem Soc Rev
January 2025
Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Strasse 4, 35043 Marburg, Germany.
For decades, advances in chiral transition metal catalysis have been closely tied to the development of customized chiral ligands. Recently, however, an alternative approach to this traditional metal-plus-chiral-ligand method has emerged. In this new strategy, chiral transition metal catalysts are composed entirely of achiral ligands, with the overall chirality originating exclusively from a stereogenic metal center.
View Article and Find Full Text PDFNat Commun
January 2025
State Key Laboratory and Institute of Elemento-Organic Chemistry, College of Chemistry, Frontiers Science Center for New Organic Matter, Haihe Laboratory of Sustainable Chemical Transformations, Nankai University 94 Weijin Road, Tianjin, China.
The diverse utility of acyclic vinylsilanes has driven the interest in the synthesis of enantioenriched vinylsilanes bearing a Si-stereogenic center. However, the predominant approaches for catalytic asymmetric generation of Si-stereogenic vinylsilanes have mainly relied on transition metal-catalyzed reactions of alkynes with different silicon sources. Here we successfully realize the enantioselective synthesis of linear silicon-stereogenic vinylsilanes with good yields and enantiomeric ratios from simple alkenes under rhodium catalysis.
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