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

页码：5441 / 5446

页数：6

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