61173-96-4Relevant articles and documents
C-H Alkylation of Aldehydes by Merging TBADT Hydrogen Atom Transfer with Nickel Catalysis
Murugesan, Vetrivelan,Ganguly, Anirban,Karthika, Ardra,Rasappan, Ramesh
supporting information, p. 5389 - 5393 (2021/07/21)
Catalyst controlled site-selective C-H functionalization is a challenging but powerful tool in organic synthesis. Polarity-matched and sterically controlled hydrogen atom transfer (HAT) provides an excellent opportunity for site-selective functionalization. As such, the dual Ni/photoredox system was successfully employed to generate acyl radicals from aldehydes via selective formyl C-H activation and subsequently cross-coupled to generate ketones, a ubiquitous structural motif present in the vast majority of natural and bioactive molecules. However, only a handful of examples that are constrained to the use of aryl halides are developed. Given the wide availability of amines, we developed a cross-coupling reaction via C-N bond cleavage using the economic nickel and TBADT catalyst for the first time. A range of alkyl and aryl aldehydes were cross-coupled with benzylic and allylic pyridinium salts to afford ketones with a broad spectrum of functional group tolerance. High regioselectivity toward formyl C-H bonds even in the presence of α-methylene carbonyl or α-amino/oxy methylene was obtained.
FUSED TRICYCLIC COMPOUNDS AND USES THEREOF IN MEDICINE
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Paragraph 00454, (2019/01/05)
The present invention relates to a fused tricyclic compound and use thereof as a medicament, in particular as a medicament for the treatment and/or prevention of hepatitis B. Specifically, the invention relates to a compound having Formula (I) or a stereoisomer, a tautomer, an N-oxide, a solvate, a metabolite, a pharmaceutically acceptable salt or a prodrug thereof, wherein each variate is as defined in specification. The invention also relates to the use of the compound having Formula (I) or a stereoisomer, a tautomer, an N-oxide, a solvate, a metabolite, a pharmaceutically acceptable salt or a prodrug thereof as a medicament, especially as a medicament for the treatment and/or prevention of hepatitis B.
Generation of 2-(Trimethylsiloxy)allyl Cations and Their Reactions with 1,3-Dienes. Change in Mechanism of 3 + 4 -> 7 Cycloaddition with Solvent
Shimizu, Nobujiro,Tanaka, Masayuki,Tsumo, Yuho
, p. 1330 - 1340 (2007/10/02)
A series of 12 different 2-(trimethylsiloxy)allyl cations 34a-l is generated from various 2-(trimethylsiloxy)allyl chlorides (3-5) with silver perchlorate.In nitromethane solution, all the cations smoothly react with furan and cyclopentadiene in a 3 + 4 -> 7 manner to give a comprehensive series of 8-oxabicyclooct-6-en-3-ones and bicyclooct-6-en-3-ones in good yields.The cycloaddition with furan proceeds in a stereospecific manner with the retention of allyl cation configurations, in accord with a concerted mechanism.The 3 + 4 -> 7 reactions in THF/ether contrast with those in nitromethane in the following ways. (1) The yield of the adducts strongly depends on the strusture of the allyl cations. (2) The reaction with furan is nonstereospecific. (3) An electrophilic substitution reaction strongly compets with the cycloaddition. (4) The cycloaddition between the cation 34a and 2-methylfuran is highly regioselective (11/12 = 19) as compared to that in nitromethane (the ratio being only 1.9).These findings in THF/ether are reasonably explained by a stepwise mechanism via an intermediate 40.Reactions with acyclic dienes (isoprene and 2,3-dimethylbutadiene), naphthalene, anisole, and methanol are also described.
