Reaction of (eta(5)-Ph(5)C(5))Ru(CO)(2)(Ot-Bu) with 5-hexen-2-ol produces two diastereomers of an alkoxycarbonyl complex having the double bond coordinated to ruthenium. The complexes were characterized by (1)H and (13)C NMR spectroscopy and in situ FT-IR measurements. The (13)C NMR carbonyl peaks of the complexes appear at 203.48, 203.55, and 204.0 ppm in a ratio of 1:1:2. IR peaks for CO and acyl were detected at 1982 (CO) and 1644 (acyl) cm(-1).
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http://dx.doi.org/10.1021/ja905741w | DOI Listing |
Org Lett
January 2025
Key Laboratory of Applied Surface and Colloid Chemistry, Ministry of Education, and School of Chemistry and Chemical Engineering, Shaanxi Normal University, Xi'an 710119, China.
Carbonylation of aryl electrophiles is an important method for constructing aromatic carbonyl compounds for materials science and pharmaceutical applications. However, there have been few studies on the carbonylation of abundant, inexpensive aryl chlorides. Moreover, the existing carbonylation methods usually require a high temperature, control of the CO pressure, and structurally complex catalysts and ligands.
View Article and Find Full Text PDFNat Commun
December 2024
Key Laboratory of Phytochemistry and Natural Medicines, Kunming Institute of Botany, Chinese Academy of Sciences, Kunming, China.
The functionalized polycycle with densely contiguous tertiary stereocenters is a formidable challenge in synthesizing the parvistemoline family of Stemona alkaloids. We herein report their catalytic, asymmetric total syntheses in 13-14 steps from commercially available 2-(methoxycarbonyl)-pyrrole, featuring the development and deployment of an Ir/Pd-synergistically-catalyzed allylation of α-non-substituted keto esters with secondary aryl-substituted alcohols, stereodivergently accessible to four stereoisomers. Using chiral Pd-enolate and Ir π-allyl complex under neutral conditions, no epimerization occurs.
View Article and Find Full Text PDFAngew Chem Int Ed Engl
October 2024
Department of Chemistry, Indian Institute of Science Education and Research Bhopal, Bhopal Bypass Road, Bhauri, Bhopal-, 462 066, India.
Herein, for the first time, we disclose the gold-catalyzed alkoxy-carbonylation of aryl and vinyl iodides utilizing ligand-enabled Au(I)/Au(III) redox catalysis. The present methodology is found to be general, efficient, employs mild reaction conditions and showcases a broad substrate scope even with structurally complex molecules. Density functional theory (DFT) calculations revealed mechanistic pathways distinct from those of conventional transition metal-catalyzed carbonylation reactions.
View Article and Find Full Text PDFACS Catal
April 2024
Department of Spectroscopy and Catalysis, Institute for Molecules and Materials, Radboud University Nijmegen, Heyendaalseweg 135, Nijmegen 6525 AJ, The Netherlands.
Palladium-catalyzed carbonylation is a versatile method for the synthesis of various aldehydes, esters, lactones, or lactams. Alkoxycarbonylation of alkenes with carbon monoxide and alcohol produces either saturated or unsaturated esters as a result of two distinct catalytic cycles. The existing literature presents an inconsistent account of the procedures favoring oxidative carbonylation products.
View Article and Find Full Text PDFNat Commun
March 2023
School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, 430074, Wuhan, China.
Switchable catalysis promises exceptional efficiency in synthesizing polymers with ever-increasing structural complexity. However, current achievements in such attempts are limited to constructing linear block copolymers. Here we report a visible light regulated switchable catalytic system capable of synthesizing hyperbranched polymers in a one-pot/two-stage procedure with commercial glycidyl acrylate (GA) as a heterofunctional monomer.
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