1. Palladium-Catalyzed Aerobic Synthesis of Terminal Acetals from Vinylarenes Assisted by π-Acceptor Ligands
- Author
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Matsumura, Satoko, Sato, Ruriko, Nakaoka, Sonoe, Yokotani, Wakana, Murakami, Yuka, Kataoka, Yasutaka, and Ura, Yasuyuki
- Subjects
chemistry.chemical_element ,010402 general chemistry ,Photochemistry ,01 natural sciences ,Chloride ,Medicinal chemistry ,Catalysis ,Dissociation (chemistry) ,Inorganic Chemistry ,Nucleophile ,medicine ,ligand effects ,Physical and Theoretical Chemistry ,quinones ,010405 organic chemistry ,Ligand ,Chemistry ,Organic Chemistry ,Electron deficiency ,palladium ,Acceptor ,0104 chemical sciences ,electron-deficient compounds ,synthetic methods ,medicine.drug ,Palladium - Abstract
This is the peer reviewed version of the following article: [http://onlinelibrary.wiley.com/doi/10.1002/cctc.201601517/abstract], which has been published in final form at [http://dx.doi.org/10.1002/cctc.201601517]. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving. 本論文はWilleyのSelf Archiving Policy により、出版の一年後の2018年2月22日公開予定です。, Terminal acetals were synthesized from various vinylarenes and 1,2- or 1,3-diols using a simple PdCl2(MeCN)2/methoxy- p-benzoquinone (MeOBQ)/CuCl catalyst system and 1 atm of O2 under mild reaction conditions by the anti-Markovnikov nucleophilic attack of an oxygen nucleophile on the coordinated vinylarenes. Cyclic α,β-unsaturated carbonyl compounds such as MeOBQ and N-phenylmaleimide were especially effective as additives to afford higher yields of the desired terminal acetals. Kinetic experiments indicated that MeOBQ operates as a π-acceptor ligand for Pd to accelerate the reaction and that the dissociation of a chloride ion from Pd precedes the rate-determining step.
- Published
- 2017