124888-60-4Relevant articles and documents
Lewis Base Catalyzed Dioxygenation of Olefins with Hypervalent Iodine Reagents
Pan, Liangkun,Ke, Zhihai,Yeung, Ying-Yeung
, p. 8174 - 8178 (2021/10/25)
1,2-Diols are extremely useful building blocks in organic synthesis. Hypervalent iodine reagents are useful for the vicinal dihydroxylation of olefins to give 1,2-diols under metal-free conditions, but strongly acidic promoters are often required. Herein, we report a catalytic vicinal dioxygenation of olefins with hypervalent iodine reagents using Lewis bases as catalysts. The conditions are mild and compatible with various functional groups.
Iron-Catalyzed Diborylation of Unactivated Aliphatic gem-Dihalogenoalkenes: Synthesis of 1,2-Bis(boryl)alkanes
Feng, Zhang,Liu, Zhengli,Pu, Yu,Zhang, Xiaoming,Zhou, Shangsheng,Zhu, Jiang
, p. 5565 - 5570 (2021/07/31)
Herein, we report the first example of iron-catalyzed defluoroborylation of unactivated gem-difluoroalkenes, gem-dichloroalkenes, and gem-dibromoalkenes, providing the 1,2-bis(boryl)alkanes in moderate to good yield. This transformation has high regiosele
Direct Synthesis of Free α-Amino Acids by Telescoping Three-Step Process from 1,2-Diols
Inada, Haruki,Shibuya, Masatoshi,Yamamoto, Yoshihiko
supporting information, p. 709 - 713 (2019/01/25)
A practical telescoping three-step process for the syntheses of α-amino acids from the corresponding 1,2-diols has been developed. This process enables the direct synthesis of free α-amino acids without any protection/deprotection step. This method was also effective for the preparation of a 15N-labeled α-amino acid. 1,2-Diols bearing α,β-unsaturated ester moieties afforded bicyclic α-amino acids through intramolecular [3 + 2] cycloadditions. A preliminary study suggests that the resultant α-amino acids are resolvable by aminoacylases with almost complete selectivity.
Site-Selective Mono-Oxidation of 1,2-Bis(boronates)
Yan, Lu,Morken, James P.
supporting information, p. 3760 - 3763 (2019/05/24)
Site-selective oxidation of vicinal bis(boronates) is accomplished through the use of trimethylamine N-oxide in 1-butanol solvent. The reaction occurs with good efficiency and selectivity across a range of substrates, providing 2-hydro-1-boronic esters which are shown to be versatile intermediates in the synthesis of chiral building blocks.
Palladium-Catalyzed meta-C-H Olefination of Arene-Tethered Diols Directed by Well-Designed Pyrimidine-Based Group
Fang, Siqiang,Wang, Xiaobing,Yin, Fucheng,Cai, Pei,Yang, Huali,Kong, Lingyi
supporting information, (2019/03/19)
The palladium-catalyzed meta-olefination of arene-tethered diols attached to a well-designed pyrimidine moiety is presented. Applications of the protocol are illustrated by the synthesis of various diol-based natural products, such as coumarins, phenylpropanoids, stilbenes, and chalcones. Advantages of this method are demonstrated through the easy removal of the template and a gram-scale olefination reaction. Finally, experimental verification, including 1H NMR, ESI-MS and IR, and DFT studies are undertaken to elucidate the mechanistic complexity.
Replacement of the Benzylpiperidine Moiety with Fluorinated Phenylalkyl Side Chains for the Development of GluN2B Receptor Ligands
Thum, Simone,Schepmann, Dirk,Kalinin, Dmitrii V.,Ametamey, Simon M.,Wünsch, Bernhard
, p. 2522 - 2529 (2018/11/23)
The 4-benzylpiperidine moiety is a central structural element of potent N-methyl-d-aspartate (NMDA) receptor antagonists containing the GluN2B subunit. To obtain novel GluN2B ligands suitable for positron emission tomography, the benzylpiperidine moiety was replaced with fluorinated ω-phenylalkylamino groups. For this purpose three primary propyl- and butylamines 7 a–c and one butyraldehyde 7 d bearing a fluorine atom and an ω-phenyl moiety were prepared in 3- to 7-step syntheses. Compounds 7 a–d were attached to various scaffolds of potent GluN2B antagonists (scaffold hopping) instead of the original 4-benzylpiperidine moiety. Although benzoxazol-2-ones and indoles with a benzylpiperidine moiety show high GluN2B affinity, the corresponding fluorophenylalkylamine derivatives did not result in high Glu2B affinity. Moderate GluN2B affinity was observed for a 3-(fluoroalkyl)-substituted tetrahydro-1H-3-benzazepine (Ki=239 nm). However, high GluN2B affinity was obtained for the tetrahydro-5H-benzo[7]annulen-7-amines 12 a–c (Ki=17–30 nm). Docking studies resulted in the same binding pose for 12 a as for the lead compound Ro 25-6981. It can be concluded that some GluN2B ligands (benzoxazolones, indoles) do not tolerate replacement of the 4-benzylpiperidine moiety with flexible fluorinated phenylalkyl side chains, but other scaffolds such as tetrahydro-3-benzazepines and -benzo[7]annulenes retain interaction with NMDA receptors containing the GluN2B subunit.
Silver(I)-Catalyzed Widely Applicable Aerobic 1,2-Diol Oxidative Cleavage
Zhou, Zhong-Zhen,Liu, Mingxin,Lv, Leiyang,Li, Chao-Jun
supporting information, p. 2616 - 2620 (2018/02/13)
The oxidative cleavage of 1,2-diols is a fundamental organic transformation. The stoichiometric oxidants that are still predominantly used for such oxidative cleavage, such as H5IO6, Pb(OAc)4, and KMnO4, generate stoichiometric hazardous waste. Herein, we describe a widely applicable and highly selective silver(I)-catalyzed oxidative cleavage of 1,2-diols that consumes atmospheric oxygen as the sole oxidant, thus serving as a potentially greener alternative to the classical transformations.
Dual Rh?Ru Catalysts for Reductive Hydroformylation of Olefins to Alcohols
Rodrigues, Fábio M. S.,Kucmierczyk, Peter K.,Pineiro, Marta,Jackstell, Ralf,Franke, Robert,Pereira, Mariette M.,Beller, Matthias
, p. 2310 - 2314 (2018/07/31)
An active and selective dual catalytic system to promote domino hydroformylation–reduction reactions is described. Apart from terminal, di- and trisubstituted olefins, for the first time the less active internal C?C double bond of tetrasubstituted alkenes can also be utilized. As an example, 2,3-dimethylbut-2-ene is converted into the corresponding n-alcohol with high yield (90 %) as well as regio- and chemoselectivity (>97 %). Key for this development is the use of a combination of Rh complexes with bulky monophosphite ligands and the Ru-based Shvo's complex. A variety of aromatic and aliphatic alkenes can be directly used to obtain mainly linear alcohols.
Aerobic Acetoxyhydroxylation of Alkenes Co-catalyzed by Organic Nitrite and Palladium
Chen, Xian-Min,Ning, Xiao-Shan,Kang, Yan-Biao
supporting information, p. 5368 - 5371 (2016/11/02)
An aerobic acetoxyhydroxylation of alkenes cooperatively catalyzed by organic nitrite and palladium at room temperature using clean and cheap air as the sole oxidant has been developed. Various vicinal diols, diacetoxyalkanes, and dihalogenoalkanes have been synthesized. The gram-scale synthesis has also been approached. Vicinal difluorination and dichlorolation products have also been achieved via this reaction.
Osmium on chelate resin: Nonvolatile catalyst for the synthesis of DIOLS from alkenes
Monguchi, Yasunari,Wakayama, Fumika,Takada, Hitoshi,Sawama, Yoshinari,Sajiki, Hironao
supporting information, p. 700 - 704 (2015/03/14)
Osmium tetraoxide (OsO4) was immobilized on a commercially available chelate resin DIAION CR11 (CR11) just by simply immersing it in a methanol solution of OsO4 at room temperature. The resulting purple solid, 5% Os/CR11, indicated no volatility, and effectively catalyzed the oxidation of various alkenes to the corresponding diols.
