Maezaki Naoyoshi, Yagi Suguru, Yoshigami Ryoko, Maeda Jun, Suzuki Tomoko, Ohsawa Shizuka, Tsukamoto Kouji, Tanaka Tetsuaki
Graduate School of Pharmaceutical Sciences, Osaka University, 1-6 Yamadaoka, Suita, Osaka 565-0871, Japan.
J Org Chem. 2003 Jul 11;68(14):5550-8. doi: 10.1021/jo034108j.
Unprecedented Pd-catalyzed sulfinylzincation with 1-alkynyl sulfoxide as a sulfinyl source was developed. Bis-sulfinyl alkenes were formed in good yields on treatment of 1-alkynyl sulfoxides with Et(2)Zn in the presence of a Pd-catalyst, wherein zinc sulfenate (or sulfinylzinc) species would be generated in situ to undergo highly syn-selective conjugate addition to the 1-alkynyl sulfoxides. By using 3,3-dimethyl-1-butynyl sulfoxides, formation of the bis-sulfinyl alkenes was completely suppressed and the sulfinylzincation of activated alkynes was accomplished. The reaction tolerates various functionalities, and was promoted considerably by the neighboring group participation of the heteroatom at the delta-position in the alkynoates. Stereodivergent synthesis of two diastereomeric vinylic sulfoxides and reaction of the resulting vinylzinc species with electrophiles were also described.
开发了一种前所未有的钯催化的亚磺酰锌化反应，该反应以1-炔基亚砜作为亚磺酰基源。在钯催化剂存在下，用Et(2)Zn处理1-炔基亚砜时，双亚磺酰基烯烃能以良好的产率生成，其中亚磺酸锌（或亚磺酰锌）物种会原位生成，以对1-炔基亚砜进行高度顺式选择性共轭加成。通过使用3,3-二甲基-1-丁炔基亚砜，双亚磺酰基烯烃的形成被完全抑制，并且实现了活性炔烃的亚磺酰锌化反应。该反应能耐受各种官能团，并且在炔酸酯中δ位杂原子的邻基参与作用下得到显著促进。还描述了两种非对映体乙烯基亚砜的立体发散合成以及所得乙烯基锌物种与亲电试剂的反应。
