A unique family of chiral peraza N -macrocyclic ligands, which are conformationally rigid and have a tunable saddle-shaped cavity, is described. Utilizing their manganese(I) complexes, the first example of earth-abundant transition metal-catalyzed asymmetric formal anti-Markovnikov hydroamination of allylic alcohols was realized, providing a practical access to synthetically important chiral γ-amino alcohols in excellent yields and enantioselectivities (up to 99 % yield and 98 % ee). The single-crystal structure of a Mn complex indicates that the manganese atom coordinates with the chiral dialkylamine moiety in a bidentate fashion. Further DFT calculations revealed that five of the six nitrogen atoms in the ligand were engaged in multiple noncovalent interactions with Mn, an isopropanol molecule, and a β-amino ketone intermediate via coordination, hydrogen bonding, and/or CH⋅⋅⋅π interactions in the transition state, showing a remarkable role of the macrocyclic framework.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1002/anie.202202972 | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
Vacuum energy in non-supersymmetric quasi-realistic heterotic-string vacua with fixed moduli.
Eur Phys J C Part Fields
February 2025
Department of Mathematical Sciences, University of Liverpool, Liverpool, L69 7ZL UK.
Recently, Baykara et al. (The Quasicrystalline string landscape, 2024; New non-supersymmetric tachyon-free strings, 2024) discussed the existence of quasicrystalline string vacua that contain a single neutral moduli, the dilaton, and studied compactifications of the non-supersymmetric heterotic-string on these spaces. We discuss a specific class of quasi-realistic string vacua with similar properties that has been known since the late eighties and analyse the vacuum energy in several non-supersymmetric examples that correspond to compactifications of tachyon free ten dimensional vacua as well as compactifications of tachyonic ten dimensional vacua.
View Article and Find Full Text PDFPractical Preparation of (3)-Hydroxy-5-Phenylpentanoic Acid: Asymmetric Synthesis of ()-Daphneolone and ()-Dihydroyashabushiketol, and Formal Synthesis of (3,5)-Yashabushidiol B.
Int J Mol Sci
February 2025
Research and Development Center, Molecules & Materials Co., Ltd., Daejeon 34013, Republic of Korea.
Many linear diarylpentanoids and diarylheptanoids contain a β-hydroxy ketone or 1,3-diol functionality as the structural motif. Reported herein is the asymmetric synthesis of ()-daphneolone, ()-dihydroyashabushiketol, and formal synthesis of (3,5)-yashabushidiol B as represented examples, employing readily accessible (3)-hydroxy-5-phenylpentanoic acid. The (3)-hydroxy-5-phenylpentanoic acid was conveniently prepared by the aldol addition of ()-acetyloxazolidinone with 3-phenylpropanal affording two diastereomers which were cleanly separated by silica gel column chromatography, followed by the removal of Evans auxiliary of (3',4)-imide.
View Article and Find Full Text PDFComparison of postoperative pain severity between primary and repeated cesarean section: a prospective cohort study.
BMC Anesthesiol
February 2025
School of Anesthesia, Wolaita Soddo University, P.O. Box 138, Wolaita Sodo, Ethiopia.
Background: The cesarean section was associated with moderate to severe postoperative pain. Uncertain differences exist between parturient who undergo a primary cesarean section and a repeat cesarean section in terms of post-operative pain.
Objective: To compare the degree of postoperative pain in patients who had primary and repeat cesarean sections.
Asymmetric Catalytic (3 + 2) Cyclization and Sequential Reaction to Construct Dihydrofuran- and Azepine-Based Spirooxindoles.
Org Lett
March 2025
Key Laboratory of Green Chemistry & Technology, Ministry of Education, College of Chemistry, Sichuan University, Chengdu 610064, China.
The enantioselective formal (3 + 2) cyclization and sequential reaction of 2-malononitrile-substituted oxindoles with benzaldehydes and -aminobenzaldehydes were achieved by chiral '-dioxide/metal complex Lewis acid catalysts. This protocol supplies facile and efficient access to highly functionalized chiral dihydrofuran- and azepine-based spirooxindoles. Based on the control experiments and the deuterium labeling studies, the interconversion of (3 + 2) diastereomeric intermediates under the reaction conditions and reversible 1,5-H transfer step were disclosed.
View Article and Find Full Text PDFRecent Developments in Stereoselective Reactions of Sulfoxonium Ylides.
Molecules
February 2025
School of Chemical Sciences, Dublin City University, Glasnevin, D09 V209 Dublin, Ireland.
This review probes the recent developments in stereoselective reactions within the area of sulfoxonium ylide chemistry since the early 2000s. An abundance of research has been applied to sulfoxonium ylide chemistry since its emergence in the early 1960s. There has been a continued effort since then with work in traditional areas, such as epoxidation, aziridination and cyclopropanation.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!