有機合成化学グループ： 鈴木(教)研究室（＆旧 増山研究室）

Organic Synthesis Group, Sophia University

abstracts_2016_2

Catalytic Availabilities of Lewis Acidic SnCl2: Ph3PAuCl-SnCl2 Composite-Catalyzed Successive ortho-Alkenylation/O-Alkenylation of Phenols Followed by Cyclization to 1-Benzopyrans
Atsuchi Tochigi, Kadzuoki Tsukamoto, Noriyuki Suzuki,* Yoshiro Masuyama*
Eur. J. Org. Chem. 2016, 5678-5685.
DOI: 10.1002/ejoc.201601042

Ph3PAuCl-SnCl2composite, prepared beforehand insitu from Ph3PAuCl and SnCl2, catalyzed the preparationof 1-benzopyrans from phenols and phenylacetylene. The Ph3PAuCl-SnCl2composite-catalyzed reaction was presumed to proceed via the successiveortho-alkenylation andO-alkenylation of phenols withphenylacetylene followed by the cyclization of preparedortho- andO-dialkenylatedphenol derivatives. Conveniently, all reactions with Ph3PAuCl-SnCl2composite were established without much attention to air and water. Ph3PAuCl-catalyzed nucleophilic additions of phenols tophenylacetylene with SnCl2as a Lewis acidic auxiliary agent; Ph3PAuCl-SnCl2composite-catalyzed successiveortho-alkenylation[9,10]andO-alkenylation[11,12]of phenols followed by cyclization to 1-benzopyrans.[13, 14]In addition, theortho-alkenylationcatalyzed by SnCl2itself is described, which has been found in thecourse of the study of Ph3PAuCl-SnCl2compositecatalysis.


ルイス酸性塩化スズSnCl2(II)ノ触媒活性: Ph3PAuCl-SnCl2 が触媒する連続したフェノールのオルト-アルケニル化/O-アルケニル化、それに続く環化による1-ベンゾピラン類の合成
栃木 淳志, 塚本 一興, 鈴木 教之,* 増山 芳郎*
Eur. J. Org. Chem. 2016, 5678-5685.
DOI: 10.1002/ejoc.201601042
金錯体と塩化スズ(II)から構成される系が触媒として機能し、フェノールとフェニルアセチレンから1-ベンゾピラン類を与えることを見出した。反応は、フェノールのオルト―アルケニル化と続くO-アルケニル化、それに続く環かによって進行した。