Department of Materials and Life Sciences, Faculty of Science and Technology, Sophia University
有機合成化学グループ： 鈴木(教)研究室（＆旧 増山研究室）
abstracts_2020_2
| Zirconium-Mediated Carbon-Carbon Bond Formation Reactions of 1,3-Enynes with Esters And Isocyanates Noriyuki Suzuki*, Makoto Hosoya, Tomoyuki Ono, Ayari Mochizuki, Yoshiro Masuyama J. Organomet. Chem. 2020, 923, 121410. DOI: 10.1016/j.jorganchem.2020.121410 |
| Five-membered metallacycloallene compounds, 1-zirconacyclopenta-2,3-dienes 1, derived from but-1-en-3-ynes 2 and low-valent zirconocene, reacted with esters and isocyanates. Reactions of 1 with carboxylic esters such as ethyl acetate and methyl benzoate resulted in the formation of alkynyl ketones after hydrolysis, albeit in low yields, and diethyl carbonate gave alkynyl esters in moderate yields. Insertion of isocyanates such as phenylisocyanate to the Zr-C bond of 1 afforded an alkynyl amide when 1 had substituents at the 2,4-positions (1a), while the zirconium complexes 1 that had silyl groups at the 2,5-positions, 1b and 1c, gave dienyl amides after hydrolysis. These reactions involved C=O insertion into the Zr-Csp3 bond in1. It is likely that the insertion afforded seven-membered 1-oxa-2-zirconacyclohepta-3,4-diene intermediates first, whilst the reaction of 2,5-disilyl-1-zirconacyclopenta-2,3-dienes 1b-c with isocyanates formed five-membered 1-oxa-2-zirconacyclopent-3-ene intermediates. Additional C-C bond formation reactions of these intermediates via transmetallation to copper salts followed by addition of allyl halides furnished allylated products. |
 |
| ジルコニウムが介在する1,3-エンインとエステル、イソシアン酸エステルとの炭素-炭素結合生成反応 鈴木 教之,* 細谷 誠, 小野 智之, 望月 菖里, 増山 芳郎 J. Organomet. Chem. 2020, 923, 121410. DOI: 10.1016/j.jorganchem.2020.121410 |
| 低原子価ジルコノセン錯体と1,3-共役エンインから形成する五員環アレン化合物の炭素炭素結合生成反応について検討した。炭酸エステル、イソシアン酸エステルとの反応で、エステル、アミドが得られた。 |