Discovery of a Formal Dyotropic Rearrangement during Acid-Mediated Dioxabicyclo[4.2.1]nonanone Formation

被引：0
|
作者：
Hashimoto, Yoshimitsu [1 ,2 ]
Kong, Wang-Yeuk [2 ]
Tantillo, Dean J. [2 ]
机构：
[1] Showa Pharmaceut Univ, Machida, Tokyo 1948543, Japan
[2] Univ Calif Davis, Dept Chem, Davis, CA 95616 USA
来源：
ORGANIC LETTERS | 2024年 / 26卷 / 26期
基金：
美国国家科学基金会;
关键词：
ADJUSTED PSEUDOPOTENTIALS; FRIEDEL-CRAFTS; ELEMENTS; MECHANISMS; ACIDITIES; SUPPORT; PATH;
D O I：
10.1021/acs.orglett.4c01616
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
A new reaction mechanism for the construction of dioxabicyclo[4.2.1]nonanone skeletons via a cation cascade has been proposed and examined by DFT and ab initio computations. This mechanism features the following steps: (1) intramolecular Friedel-Crafts-type cyclization with a methyl oxocarbenium cation formed by carboxylate disconnection, (2) electron-rich aromatic ring assisted methoxide loss followed by lactone formation, and (3) stepwise dyotropic rearrangement resulting in skeletal isomerization from a dioxabicyclo[3.2.2]nonanone to the dioxabicyclo[4.2.1]nonanone product observed experimentally. The high regioselectivity and driving force for the overall rearrangement were rationalized, and Lewis and Br & oslash;nsted acid mediated reactivities were compared.
引用
收藏
页码：5441 / 5446
页数：6
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