7116-38-3Relevant articles and documents
Radical dehydroxylative alkylation of tertiary alcohols by Ti catalysis
Xie, Hao,Guo, Jiandong,Wang, Yu-Quan,Wang, Ke,Guo, Peng,Su, Pei-Feng,Wang, Xiaotai,Shu, Xing-Zhong
supporting information, p. 16787 - 16794 (2020/11/09)
Deoxygenative radical C?C bond-forming reactions of alcohols are a long-standing challenge in synthetic chemistry, and the current methods rely on multistep procedures. Herein, we report a direct dehydroxylative radical alkylation reaction of tertiary alcohols. This new protocol shows the feasibility of generating tertiary carbon radicals from alcohols and offers an approach for the facile and precise construction of all-carbon quaternary centers. The reaction proceeds with a broad substrate scope of alcohols and activated alkenes. It can tolerate a wide range of electrophilic coupling partners, including allylic carboxylates, aryl and vinyl electrophiles, and primary alkyl chlorides/bromides, making the method complementary to the cross-coupling procedures. The method is highly selective for the alkylation of tertiary alcohols, leaving secondary/primary alcohols (benzyl alcohols included) and phenols intact. The synthetic utility of the method is highlighted by its 10-g-scale reaction and the late-stage modification of complex molecules. A combination of experiments and density functional theory calculations establishes a plausible mechanism implicating a tertiary carbon radical generated via Ti-catalyzed homolysis of the C?OH bond.
Anodic benzylic C(sp3)-H amination: Unified access to pyrrolidines and piperidines
Herold, Sebastian,Bafaluy, Daniel,Mu?iz, Kilian
supporting information, p. 3191 - 3196 (2018/07/29)
An electrochemical aliphatic C-H amination strategy was developed to access the important heterocyclic motifs of pyrrolidines and piperidines within a uniform reaction protocol. The mechanism of this unprecedented C-H amination strategy involves anodic C-H activation to generate a benzylic cation, which is efficiently trapped by a nitrogen nucleophile. The applicability of the process is demonstrated for 40 examples comprising both 5- and 6-membered ring formations.
Assembly and post-modification of a metal-organic nanotube for highly efficient catalysis
Kong, Guo-Qiang,Ou, Sha,Zou, Chao,Wu, Chuan-De
, p. 19851 - 19857 (2013/02/22)
A metal-organic nanotube (MONT) was synthesized by linking up the bent organic ligands and the tetra-coordinated zinc cations under mild conditions. Structural analysis revealed that the MONT has a very large exterior wall diameter of 4.91 nm and an interior channel diameter of 3.32 nm. Interlocking of the nanotubes gives rise to a 3D chiral framework containing 1D helical cylindered channels with diameter of 2.0 nm. The MONT has very interesting property by synergizing the functionality of nanotubes, metal-organic frameworks (MOFs), and N-heterocyclic carbenes (NHCs). The dye adsorption experiments demonstrate that the channels of the MONTs are accessible to large reagents typically used for catalysis. The postmodification of the MONT can be easily operated by unmarking the imidazolium moieties in the channel walls, which was conducted as a highly active heterogeneous catalyst for Suzuki-Miyaura and Heck coupling reactions, hydrogenation of olefins and nitrobenzene, while the constituent elements are less efficient for these reactions under the same conditions.
