101306-31-4Relevant articles and documents
Regioselectivity of the ring opening in the reaction of phenyloxirane, (phenylmethyl)oxirane and (2-phenylethyl)oxirane with K-, K+(15-crown-5)2
Grobelny, Zbigniew,Stolarzewicz, Andrzej,Morejko-Buz, Barbara,Maercker, Adalbert,Krompiec, Stanis?aw,Bieg, Tadeusz
, p. 43 - 51 (2003)
The electron from potassium anion of K-, K+ (15-crown-5)2 (1) is initially transferred to the aromatic ring of phenyloxirane and (phenylmethyl)oxirane. The oxirane ring is then opened exclusively in the α-position. Two dimeric products, i.e. dipotassium 2,3-diphenylbutane-1,4-dioxide and dipotassium 1,3-diphenylbutane-1,4-dioxide are formed in the case of phenyloxirane. A mixture of several potassium alkoxides involving 3-phenylpropoxide, 3-phenylallyloxide, tetraethylene glycoxide vinyl ether, and appropriate alcohols, i.e. 3-phenyl-1-propanol, 3-phenylallyl alcohol, and tetraethylene glycol vinyl ether, is obtained in the reaction of 1 with (phenylmethyl)oxirane. However, introduction of the second CH2 group into the substituent results in the β-opening of the oxirane ring in (2-phenylethyl)oxirane. Potassium 4-phenylbutane-2-oxide, and potassium tetraethylene glycoxide vinyl ether are the main reaction products in this case. Organometallic intermediates take part in all these processes.
Mild and efficient aryl-alkenyl coupling via Pd(II) catalysis in the presence of oxygen or Cu(II) oxidants
Parrish, Jay P.,Jung, Young Chun,Shin, Seung Il,Jung, Kyung Woon
, p. 7127 - 7130 (2002)
We report herein a mild and efficient method for carbon-carbon bond formation between aryl stannanes and olefins via Pd(II) catalysis in the presence of oxygen or Cu(II) oxidants as a reoxidant. The process allows reactions between various olefins and aryl stannanes of varying electron density. Coupling methods under these oxidation conditions are comparatively described, and the benefits and limitations are also discussed.
Mix-and-heat benzylation of alcohols using a bench-stable pyridinium salt
Poon, Kevin W. C.,Dudley, Gregory B.
, p. 3923 - 3927 (2006)
2-Benzyloxy-1-methylpyridinium inflate (1) is a stable, neutral organic salt that converts alcohols into benzyl ethers upon warming. The synthesis and reactivity of 1 are described herein. Benzylation of a wide range of alcohols occurs in good to excellent yield.
Copper-Catalyzed Transfer Hydrodeuteration of Aryl Alkenes with Quantitative Isotopomer Purity Analysis by Molecular Rotational Resonance Spectroscopy
Alansari, Isabella Y.,Clark, Joseph R.,Holdren, Martin S.,Neill, Justin L.,Pate, Brooks H.,Reyes, Albert,Sloane, Samantha E.,Sonstrom, Reilly E.,Vang, Zoua Pa
supporting information, p. 7707 - 7718 (2021/06/21)
A copper-catalyzed alkene transfer hydrodeuteration reaction that selectively incorporates one hydrogen and one deuterium atom across an aryl alkene is described. The transfer hydrodeuteration protocol is selective across a variety of internal and terminal alkenes and is also demonstrated on an alkene-containing complex natural product analog. Beyond using 1H, 2H, and 13C NMR analysis to measure reaction selectivity, six transfer hydrodeuteration products were analyzed by molecular rotational resonance (MRR) spectroscopy. The application of MRR spectroscopy to the analysis of isotopic impurities in deuteration chemistry is further explored through a measurement methodology that is compatible with high-throughput sample analysis. In the first step, the MRR spectroscopy signatures of all isotopic variants accessible in the reaction chemistry are analyzed using a broadband chirped-pulse Fourier transform microwave spectrometer. With the signatures in hand, measurement scripts are created to quantitatively analyze the sample composition using a commercial cavity enhanced MRR spectrometer. The sample consumption is below 10 mg with analysis times on the order of 10 min using this instrument - both representing order-of-magnitude reduction compared to broadband MRR spectroscopy. To date, these measurements represent the most precise spectroscopic determination of selectivity in a transfer hydrodeuteration reaction and confirm that product regioselectivity ratios of >140:1 are achievable under this mild protocol.
Photo-induced Decarboxylative Heck-Type Coupling of Unactivated Aliphatic Acids and Terminal Alkenes in the Absence of Sacrificial Hydrogen Acceptors
Cao, Hui,Jiang, Heming,Feng, Hongyu,Kwan, Jeric Mun Chung,Liu, Xiaogang,Wu, Jie
supporting information, p. 16360 - 16367 (2018/11/27)
1,2-Disubstituted alkenes such as vinyl arenes, vinyl silanes, and vinyl boronates are among the most versatile building blocks that can be found in every sector of chemical science. We herein report a noble-metal-free method of accessing such olefins through a photo-induced decarboxylative Heck-type coupling using alkyl carboxylic acids, one of the most ubiquitous building blocks, as the feedstocks. This transformation was achieved in the absence of external oxidants through the synergistic combination of an organo photo-redox catalyst and a cobaloxime catalyst, with H2 and CO2 as the only byproducts. Both control experiments and DFT calculations supported a radical-based mechanism, which eventually led to the development of a selective three-component coupling of aliphatic carboxylic acids, acrylates, and vinyl arenes. More than 90 olefins across a wide range of functionalities were effectively synthesized with this simple protocol.
