114378-07-3Relevant academic research and scientific papers
Palladium-catalyzed C(sp3)-C(sp2) cross-coupling of homoleptic rare-earth metal trialkyl complexes with aryl bromides: Efficient synthesis of functionalized benzyltrimethylsilanes
Cai, Guilong,Huang, Yingda,Du, Tingting,Zhang, Shaowen,Yao, Bo,Li, Xiaofang
, p. 5425 - 5427 (2016)
The first C(sp3)-C(sp2) cross-coupling of rare-earth metal alkyl complexes with aryl bromides has been developed. This reaction was conducted at low catalyst loading (0.5 mol%) and exhibited a broad substrate scope, thus providing a facile method for the synthesis of benzyltrimethylsilanes with diverse functional groups.
Fluoroalkylselenolation of Alkyl Silanes/Trifluoroborates under Metal-Free Visible-Light Photoredox Catalysis
Ghiazza, Clément,Khrouz, Lhoussain,Billard, Thierry,Monnereau, Cyrille,Tlili, Anis
supporting information, p. 1559 - 1566 (2019/11/03)
Herein a metal-free fluoroalkylselenolation of alkylsilanes as well as potassium alkyltrifluoroborates under visible light photocatalysis is disclosed. The developed methodologies are performed under mild conditions, room temperature in the presence of an organic photocatalyst and blue LED irradiation. Mechanistic investigations including luminescence and EPR spectroscopy allow us to shed light on both mechanisms.
Direct oxidation of the C(sp2)-C(sp3) bond from benzyltrimethylsilanes to phenols
Li, Wei,Gao, Guolin,Gao, Yuan,Yang, Chao,Xia, Wujiong
supporting information, p. 5291 - 5293 (2017/07/10)
A novel pathway for direct conversion of benzylsilanes to phenols by oxidation with Na2S2O8 and oxygen is efficiently developed under mild and neutral conditions. The reaction shows good functional group tolerance to afford phenols in moderate yields. The possible mechanism is proposed based on the isotopic labeling trials.
Nickel-Catalyzed Cross-Coupling of Anisoles with Alkyl Grignard Reagents via C-O Bond Cleavage
Tobisu, Mamoru,Takahira, Tsuyoshi,Chatani, Naoto
supporting information, p. 4352 - 4355 (2015/09/15)
Nickel-catalyzed cross-coupling of methoxyarenes with alkyl Grignard reagents, which involves the cleavage of the C(aryl)-OMe bond, has been developed. The use of 1,3-dicyclohexylimidazol-2-ylidene as a ligand allows the introduction of a variety of alkyl groups, including Me, Me3SiCH2, ArCH2, adamantyl, and cyclopropyl. The method can also be used for the alkylative elaboration of complex molecules bearing a C(aryl)-OMe bond.
Direct catalytic cross-coupling of organolithium compounds
Giannerini, Massimo,Fananas-Mastral, Martin,Feringa, Ben L.
, p. 667 - 672 (2013/08/23)
Catalytic carbon-carbon bond formation based on cross-coupling reactions plays a central role in the production of natural products, pharmaceuticals, agrochemicals and organic materials. Coupling reactions of a variety of organometallic reagents and organic halides have changed the face of modern synthetic chemistry. However, the high reactivity and poor selectivity of common organolithium reagents have largely prohibited their use as a viable partner in direct catalytic cross-coupling. Here we report that in the presence of a Pd-phosphine catalyst, a wide range of alkyl-, aryl- and heteroaryl-lithium reagents undergo selective cross-coupling with aryl- and alkenyl-bromides. The process proceeds quickly under mild conditions (room temperature) and avoids the notorious lithium halogen exchange and homocoupling. The preparation of key alkyl-, aryl- and heterobiaryl intermediates reported here highlights the potential of these cross-coupling reactions for medicinal chemistry and material science.
Novel, strained 10b,10c-dihydropyrenes bearing bulky TMSCH2 groups at the internal positions
Sawada, Tsuyoshi,Wakabayashi, Masaki,Takeo, Hiromi,Miyazawa, Akira,Tashiro, Masashi,Thiemann, Thies,Mataka, Shuntaro
, p. 403 - 407 (2007/10/03)
Two novel, strained trans-10b,10c-dihydropyrenes, 9a-b, with internal, bulky trimethylsilylmethyl substituent(s) were synthesized. Their 14π-electron annulene systems were found to be distorted, as shown by X-ray crystallographic analyses and 1H-NMR and UV spectroscopy.
Benzylic lithium compounds: The missing link in carbon-lithium covalency. Dynamics of ion reorientation, rotation around the ring-benzyl bond, and bimolecular C-Li exchange
Fraenkel, Gideon,Martin, Kevin V.
, p. 10336 - 10344 (2007/10/02)
Benzyllithium compounds, hitherto assumed from NMR data to consist of ion pairs, have been found to exhibit spin coupling between 13C and directly bound 6Li under conditions wherein bimolecular carbon - lithium bond exchange is too slow to average the coupling constants. These conditions involved the use of species in which lithium is internally solvated or of dilute solutions (0.005 M) of benzyllithium-13C-6Li (enriched at Cα) at low temperature. The low values of 1J(13C-6Li), 3-4 Hz, imply a small detectable degree of C-Li covalence with the arrangement around Cα distorted from coplanarity. The C-Li bonds in benzyllithium are concluded to lie in a continuum of C-Li covalency between the many monomeric species in which 1J(13C-6Li) is 16 ± 1 Hz and separated ion pairs. NMR line shape analysis of data for internally solvated benzyllithium 2b provides quantitative insight into the dynamics of intramolecular reorientation of coordinated lithium with respect to the benzyl plane, rotation around the ring-Cα bond, and bimolecular carbon-lithium bond exchange, listed in order of widely different increasing rates, the activation parameters being ΔH? (kcal/mol) and ΔS? (eu) in the same order: 14 and 6.6; 6.4 and -14; 10.8 and -21.
