79271-99-1Relevant articles and documents
REACTION OF TITANOCENE ALKYLS WITH PYRIDINES; A NOVEL TYPE OF CYCLOMETALLATION REACTION
Klei, E.,Teuben, J. H.
, p. 53 - 64 (1981)
Reaction of Cp2TiR (R = alkyl) with 2-substituted-pyridines and with quinolines leads to α-metallation of these ligands with formation of triangular titanocycles containing TiIII.Proof of the metallation at the α-position comes from reactions of the complexes formed with I2 and D2O/DCl which yield the corresponding iodo- and deutero-pyridine and -quinoline derivatives.Reaction of Cp2TiR with the structurally related ligand benzalaniline leads to a side-on coordinated benzalaniline complex of titanocene.Reactions of this diamagnetic complex with I2, CO2 and H2 aredescribed.
Site-Selective Copper-Catalyzed Amination and Azidation of Arenes and Heteroarenes via Deprotonative Zincation
Hendrick, Charles E.,Bitting, Katie J.,Cho, Seoyoung,Wang, Qiu
supporting information, p. 11622 - 11628 (2017/08/30)
Arene amination is achieved by site-selective C-H zincation followed by copper-catalyzed coupling with O-benzoylhydroxylamines under mild conditions. Key to this success is ortho-zincation mediated by lithium amidodiethylzincate base that is effective for a wide range of arenes, including nonactivated arenes bearing simple functionalities such as fluoride, chloride, ester, amide, ether, nitrile, and trifluoromethyl groups as well as heteroarenes including indole, thiophene, pyridine, and isoquinoline. An analogous C-H azidation is also accomplished using azidoiodinane for direct introduction of a useful azide group onto a broad scope of arenes and heteroarenes. These new transformations offer rapid access to valuable and diverse chemical space of aminoarenes. Their broad applications in organic synthesis and drug discovery are demonstrated in the synthesis of novel analogues of natural product (-)-nicotine and antidepressant sertraline by late-stage amination and azidation reactions.
Highly selective metalations of pyridines and related heterocycles using new frustrated lewis pairs or tmp-zinc and tmp-magnesium bases with bf 3·oet2
Jaric, Milica,Haag, Benjamin A.,Unsinn, Andreas,Karaghiosoff, Konstantin,Knochel, Paul
supporting information; experimental part, p. 5451 - 5455 (2010/09/16)
(Figure Presented) Efficient and selective: Frustrated Lewis pairs based on BF3·OEt2 and LiCl-com-plexed tmpMg or tmpZn amides (tmp = 2,2,6,6-tetramethylpiperidyl) allow the efficient and regioselective metalation of various functionalized N heterocycles (see scheme for examples). Moreover, such metalations carried out in the presence or absence of BF 3·OEt2 enable a complete switch of regioselectivity, thus allowing complementary fuctionalization.
