A green way to amino acids: α-Tetrasubstituted α-amino acid derivatives are formed in high yield and enantioselectivity by using a Rh-catalyzed enantioselective alkynylation of α-ketiminoesters. This reaction, which involves a proton transfer and can be conducted at room temperature, has high substrate scope (see scheme; Cbz = benzyloxycarbonyl, Fmoc = 9-fluorenylmethyloxycarbonyl).
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http://dx.doi.org/10.1002/chem.201301237 | DOI Listing |
Adv Sci (Weinh)
November 2024
School of Chemistry and Chemical Engineering, Zhejiang Sci-Tech University, Hangzhou, 310018, China.
Chiral fully-substituted allenes are synthetically significant and pivotal building blocks that can engage in diverse transformations toward a variety of bioactive molecules. The enantioselective assembly of these skeletons using readily available reactants offers significant advantages but remains challenging. Herein, an asymmetric formal Michael-type addition of alkynyl imines with the key alkylgold intermediates derived in situ from N-propargylamides is accomplished under gold-complex and chiral quinine-derived squaramide (QN-SQA) synergetic catalysis.
View Article and Find Full Text PDFOrg Lett
November 2024
Université Paris-Saclay, Centre National de la Recherche Scientifique (CNRS), Institut de Chimie des Substances Naturelles, UPR 2301, 91198 Gif-sur-Yvette, France.
The tethered counterion-directed catalysis (TCDC) strategy enables the Au(I)-catalyzed highly enantioselective synthesis of bicyclic furan derivatives via a reaction sequence combining the cycloisomerization of 2-alkynyl enones and the addition of nucleophiles. A large range of oxygenated nucleophiles, such as water, alcohols, carboxylic acids, and peroxides, have successfully been used as nucleophiles, delivering the chiral furane derivatives in high enantioselectivities (mostly above 90% enantiomeric excess). The CPAphosAuCl complexes were used with catalytic loadings as low as 0.
View Article and Find Full Text PDFInt J Mol Sci
September 2024
Natural Compounds and Organic Synthesis Laboratory, Migal-Galilee Research Institute, Kiryat Shmona 11016, Israel.
Chiral pincer complexes, characterized by their rigid tridentate coordination framework, have emerged as powerful catalysts in asymmetric synthesis. This review provides a comprehensive overview of recent advancements in the development of chiral pincer-type ligands and their corresponding transition metal complexes. We highlight the latest progress in their application across a range of catalytic asymmetric reactions, including the (transfer) hydrogenation of polar and non-polar bonds, hydrophosphination, alkynylation, Friedel-Crafts reactions, enantioselective reductive cyclization of alkynyl-tethered cyclohexadienones, enantioselective hydrosilylation, as well as Aza-Morita-Baylis-Hillman reactions.
View Article and Find Full Text PDFChem Commun (Camb)
October 2024
The Institute of Pharmacology, School of Basic Medical Sciences, Lanzhou University, Lanzhou 730000, China.
Herein, we report an example of a stereoselective γ-addition reaction of trifluoromethyl ketimines to 1-alkynyl ketones mediated by an isothiourea, BTM, under mild conditions, which afforded tetrasubstituted allenes with central chiralities in high yields (up to 94% yield), good enantioselectivities (up to 91% ee), and excellent diastereoselectivities (all >20 : 1 dr). In addition, the BTM-catalyzed γ-addition reaction was successfully applied to the gram-scale reaction, and an unexpected benzopyrrolothiazine derivative was successfully converted, albeit racemic.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
November 2024
State Key Laboratory of Chemo/Biosensing and Chemometrics, Advanced Catalytic Engineering Research Center of the Ministry of Education, College of Chemistry and Chemical Engineering, Hunan University, Changsha, Hunan, 410082, P. R. China.
The cycloaddition reaction involving bicyclo[1.1.0]butanes (BCBs) offers a versatile and efficient synthetic platform for producing C(sp)-rich rigid bridged ring scaffolds, which act as phenyl bioisosteres.
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