An asymmetric Mannich-type addition of aldimines and haloacetonitriles is reported here, yielding halogenated aminonitriles with excellent stereoselectivity, facilitated by a pincer Ni(II) complex as a catalyst. Haloacetonitriles are recognized as reactive electrophiles, and the possibility of their use as a pronucleophile has been almost neglected for many years. The resulting adduct can be readily converted into various valuable derivatives, including chiral aziridines, starting from chlorinated compounds.
Download full-text PDF |
Source |
---|---|
http://dx.doi.org/10.1021/acs.orglett.4c02505 | DOI Listing |
Angew Chem Int Ed Engl
January 2025
Jinan University, State Key Laboratory of Bioactive Molecules and Druggability Assessment, CHINA.
Secupyritines A‒C are unique polycyclic Securinega alkaloids isolated from medicinal plant Flueggea suffruticosa. They feature a distinctive 6/6/6/5/6 fused pentacyclic ring system with a highly strained 2-oxa-6-aza[4.4.
View Article and Find Full Text PDFAdv 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
September 2024
Institute of Microbial Chemistry (BIKAKEN), 3-14-23 Kamiosaki, Shinagawa-ku, Tokyo 141-0021, Japan.
An asymmetric Mannich-type addition of aldimines and haloacetonitriles is reported here, yielding halogenated aminonitriles with excellent stereoselectivity, facilitated by a pincer Ni(II) complex as a catalyst. Haloacetonitriles are recognized as reactive electrophiles, and the possibility of their use as a pronucleophile has been almost neglected for many years. The resulting adduct can be readily converted into various valuable derivatives, including chiral aziridines, starting from chlorinated compounds.
View Article and Find Full Text PDFJ Org Chem
August 2024
N. D. Zelinsky Institute of Organic Chemistry, Russian Academy of Sciences, Leninsky Prospect, 47, Moscow 119991, Russian Federation.
A powerful synthetic strategy for the asymmetric synthesis of enantiomerically enriched γ-functionalized α-amino acid derivatives based on the highly stereoselective proline-catalyzed Mannich-type reaction of pre-prepared or -generated γ-pyrone-derived aldimines with carbonyl compounds and subsequent transformations of multifunctional reaction products has been developed. A significant positive nonlinear effect was detected for the key organocatalytic reaction. The developed strategy was applied for facile gram-scale preparation of ()-γ-oxonorvaline, used for site-specific modification of proteins, and both enantiomers of amycolatolide A recently isolated from the lichen-derived actinomycete sp.
View Article and Find Full Text PDFOrg Lett
August 2024
Yunnan Key Laboratory of Chiral Functional Substance Research and Application, Yunnan Minzu University, Yuehua Street, Kunming 650504, China.
The asymmetric Mannich-type reaction of quinoxalin-2-ones with difluoroenoxysilanes has been developed for the synthesis of chiral -difluoroalkylated quinoxalin-2-ones. The reaction worked in the presence of chiral phosphoric acid and B(CF) in THF at room temperature. The reaction exhibited a good substrate scope furnishing the products in good yields (up to 97%) with up to 96% .
View Article and Find Full Text PDFEnter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!