Iridium-catalyzed arene ortho-silylation by formal hydroxyl-directed C-H activation.
Iridium-catalyzed arene ortho-silylation by formal hydroxyl-directed C-H activation.
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DOI：
10.1021/ja1086547
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发表时间：
2010-12-08
影响因子：
15
通讯作者：
Hartwig JF
中科院分区：
文献类型：
--
作者：
Simmons EM;Hartwig JF
发展了一种芳基酮、苯甲醛和苯甲醇衍生物的邻位硅烷化反应策略，其中羟基作为红外催化芳烃C-H键活化的直接基元。以降冰片烯为氢受体，以1mol%[Ir(Cod)OMe]2和1，10-二氮杂菲为催化剂，在80~100℃的温度下，由羰基化合物或醇一锅合成(氢化)硅醚，生成苯并硅烷。通过Tamao-Fleming氧化或Hiyama交叉偶联将苯酚或联芳基衍生物转化为苯酚或联芳基衍生物，从而证明了苯并硅烷产品的合成用途。C-H硅基化产物的这两种转化都利用了体系中的Si-O键，并通过用氢氧化物而不是氟化物活化硅基部分来进行。
A strategy for the ortho-silylation of aryl ketone, benzaldehyde and benzyl alcohol derivatives has been developed in which a hydroxyl group formally serves as the directing element for Ir-catalyzed arene C-H bond activation. One-pot generation of a (hydrido)silyl ether from the carbonyl compound or alcohol is followed by dehydrogenative cyclization at 80–100 °C in the presence of norbornene as hydrogen acceptor and the combination of 1 mol % [Ir(cod)OMe]2 and 1,10-phenanthroline as catalyst to form benzoxasiloles. The synthetic utility of the benzoxasilole products is demonstrated by conversion to phenol or biaryl derivatives by Tamao-Fleming oxidation or Hiyama cross-coupling. Both of these transformations of the C-H silylation products exploit the Si-O bond in the system and proceed by activation of the silyl moiety with hydroxide, rather than fluoride.
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影响因子：
2.3
作者：
ANDO, W;SEKIGUCHI, A
通讯作者：
SEKIGUCHI, A
影响因子：
2.8
作者：
Field, LD;Messerle, BA;Hambley, TW
通讯作者：
Hambley, TW
影响因子：
4.9
作者：
Hijji, YM;Hudrlik, PF;Hudrlik, AM
通讯作者：
Hudrlik, AM
影响因子：
15
作者：
Ihara, Hideki;Suginome, Michinori
通讯作者：
Suginome, Michinori
影响因子：
15
作者：
FARNHAM, WB;DIXON, DA;GUGGENBERGER, LJ
通讯作者：
GUGGENBERGER, LJ