38384-57-5Relevant academic research and scientific papers
Chemoselective reduction of ?,￠-unsaturated carbonyl and carboxylic compounds by hydrogen iodide
Matsumoto, Shoji,Marumoto, Hayato,Akazome, Motohiro,Otani, Yasuhiko,Kaiho, Tatsuo
, p. 590 - 599 (2021/03/29)
The selective reduction of ?,￠-unsaturated carbonyl compounds was achieved to produce saturated carbonyl compounds with aqueous HI solution. The introduction of an aryl group at an ? or ￠ position efficiently facilitated the reduction with good yield. The reaction was applicable to compounds bearing carboxylic acids and halogen atoms. Through the investigation of the reaction mechanism, it was found that Michael-type addition of iodide occurred to produce ￠-iodo compounds followed by the reduction of C-I bond via anionic and radical paths.
An expeditious synthesis of tamoxifen, a representative SERM (selective estrogen receptor modulator), via the three-component coupling reaction among aromatic aldehyde, cinnamyltrimethylsilane, and β-chlorophenetole
Shiina, Isamu,Sano, Yoshiyuki,Nakata, Kenya,Suzuki, Masahiko,Yokoyama, Toshikazu,Sasaki, Akane,Orikasa, Tomoko,Miyamoto, Tomomi,Ikekita, Masahiko,Nagahara, Yukitoshi,Hasome, Yoshimune
, p. 7599 - 7617 (2008/03/14)
Two new synthetic pathways to the anti-cancer agent tamoxifen and its derivatives were developed. The first route involved the aldol reaction of benzyl phenyl ketone with acetaldehyde followed by Friedel-Crafts substitution with anisole in the presence of Cl2Si(OTf)2 to produce 1,1,2-triaryl-3-acetoxybutane, a precursor of the tamoxifen derivatives. The second one utilized the novel three-component coupling reaction among aromatic aldehydes, cinnamyltrimethylsilane, and aromatic nucleophiles using HfCl4 as a Lewis acid catalyst to produce 3,4,4-triarylbutene, that is also a valuable intermediate of the tamoxifen derivatives. The former strategy requires a total of 10 steps from the aldol formation to the final conversion to tamoxifen, whereas the latter needs only three or four steps to produce tamoxifen and droloxifene including the installation of the side-chain moiety and the base-induced double-bond migration to form the tetra-substituted olefin structure. This synthetic strategy seems to serve as a new and practical pathway to prepare not only the tamoxifen derivatives but also the other SERMs (selective estrogen receptor modulators) including estrogen-dependent breast cancer and osteoporosis agents.
Biosynthesis of Aspyrone, a Metabolite of Aspergillus melleus. Incorporation Studies with 14C- and 3H-Labelled Acetates and Malonate
Copeland, R. Jeffrey,Hill, Robert A.,Hinchcliffe, David J.,Staunton, James
, p. 1013 - 1019 (2007/10/02)
Incorporation studies with 14C-labelled acetates and malonate confirm the polyketide origin of aspyrone (1), and identify the chain starter unit.Five carbons are derived from the methyl group of acetate, and the remaining four from the carboxy group.The pattern of incorporation of tritium from acetate is inconsistent with a biosynthesis from aromatic precursors of the mellein type.Possibly advanced precursors containing a 2-methylchromone nucleus were not incorporated.The evidence suggests that aromatic precursors are not involved in aspyrone biosynthesis, and that the carbon skeleton is produced like that of the co-metabolite asperlactone (6), by decarboxylation and rearrangement of a linear pentaketide intermediate.
