Palladium-catalyzed decarboxylative cyclization of α-acyloxyketones having an allene moiety in the tether
Palladium-catalyzed decarboxylative cyclization of α-acyloxyketones having an allene moiety in the tether
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DOI：
10.1039/d2nj04657a
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发表时间：
2022-11-28
影响因子：
3.3
通讯作者：
Sato，Yoshihiro
中科院分区：
文献类型：
--
作者：
Yabuta，Akimasa;Oonishi，Yoshihiro;Sato，Yoshihiro
本文报道了钯（0）催化的α-酰氧基酮的脱羧环化反应，得到各种环己酮衍生物。DFT计算表明，该反应按如下顺序进行：（1）α-酰氧基酮1的C（α）-O键与钯（0）配合物的氧化加成，（2）末端丙二烯双键插入Pd-C（sp ~ 3）键，在羰基的α-碳和丙二烯的β-碳之间形成C-C键，（3）脱羧，（4）脱羧，（5）脱羧，（6）脱羧，（7）脱羧，（8）脱羧，（9）脱羧，（10）脱羧，（1和（4）还原消除以形成C（sp 3）-C（sp）键。DFT计算还合理化了为什么反应得到6元产物而不是5元或7元产物。
We herein report palladium(0)-catalyzed decarboxylative cyclization of α-acyloxyketones having an allene moiety in the tether, giving various cyclohexanone derivatives. DFT calculations suggested that the reaction proceeds in the following sequence: (1) oxidative addition of the C(α)–O bond of α-acyloxyketones 1 to a palladium(0) complex; (2) insertion of the terminal allene double bond into the Pd–C(sp3) bond to form a C–C bond between the α-carbon of the carbonyl group and the β-carbon in the allene; (3) decarboxylation; and (4) reductive elimination to form a C(sp3)–C(sp) bond. The DFT calculations also rationalized why the reaction gives a 6-membered product instead of a 5- or 7-membered product.