A new route to polyselenoether macrocycles. Catalytic macrocyclization of 3,3-dimethylselenatane by [Re2(CO)9]
作者:Richard D. Adams、Kenneth T. McBride
DOI:10.1039/a608481h
日期:——
3,3-Dimethylselenatane,
SeCH
2
CMe
2
CH
2
, DMSe is
cyclooligomerized catalytically at 115 °C in the presence of
[Re
2
(CO)
9
(SeCH
2
CMe
2
C
H
2
)] to yield three new polyselenoether macrocycles
3,3,7,7-tetramethyl-1,5-diselenacyclooctane,
3,3,7,7,11,11-hexamethyl-1,5,9-triselenacyclododecane,
3,3,7,7,11,11,15,15-octamethyl-1,5,9,13-tetra- selenacyclohexadecane and
polymer of DMSe; all three macrocycles are characterized
crystallographically; in all cases the gem-dimethyl groups are
directed toward the exterior of the rings; interestingly, some methylene
groups are directed to the interior.
3,3-二甲基硒杂环戊烷,即SeCH2CMe2CH2,DMSe在115°C下与[Re2(CO)9(SeCH2CMe2CH2)2]催化环聚,生成三个新的多硒醚大环,即3,3,7,7-四甲基-1,5-二硒杂环辛烷、3,3,7,7,11,11-六甲基-1,5,9-三硒杂环十二烷、3,3,7,7,11,11,15,15-八甲基-1,5,9,13-四硒杂环十六烷和DMSe聚合物。这三个大环均具有晶体学特征,在所有情况下,二甲基基团均朝向环的外侧,有趣的是,一些亚甲基基团朝向环的内侧。