摘要：Kyoka Sakamoto, Kazunori Miyamoto,* Masataka Kubota,TadafumiMatsunaga, Shinichiro Kamino, and Masanobu Uchiyama*
转自：康龙化成
-decarboxylation of Aliphatic Carboxylic Acids with
PhI
(
OAc
)
2
and CHI
3
under Ambient Conditions
Kyoka Sakamoto, Kazunori Miyamoto,* Masataka Kubota, Tadafumi Matsunaga, Shinichiro Kamino, and Masanobu Uchiyama*
Miyamoto − Graduate School of Pharmaceutical Sciences, The University of Tokyo, Tokyo 113-0033, Japan; Faculty of Pharmacy, Keio University, Tokyo 105-8512, Japan; School of Pharmacy, Aichi GakuinUniversity, Nagoya 464-8650, Japan;
—Org. Lett. 2025DOI: 10.1021/acs.orglett.5c00924
KEYWORDS: decarboxylation,iodination,photochemistry (反应类型), carboxylic acids (原料), alkyl iodide (产物), C(sp3)–I (成键类型), PhI(OAc)2, CHI3, fluorescent light (其他)
ABSTRACT: We have developed a mild and practical synthesis of primary, secondary and tertiary alkyl iodides by
iododecarboxylation
(decarboxylative iodination) of the corresponding carboxylic acids using (
diacetoxyiodo
)benzene and iodoform under ambient conditions. The method does not require heating or intense light irradiation and can be used to install iodine at the bridgehead position of strained cycloalkanes, as well as in a variety of alkanes with complex frameworks/functionalities.
Background and This Work:
Mechanistic Proposal
Prof. Masanobu Uchiyama and his co-workers havedeveloped an efficient method for the iodo-decarboxylation of primary, secondary, and tertiary alkyl carboxylic acidswith readily available PhI(OAc)2 and CHI3. This iodo-decarboxylation proceeds smoothly under air, at room temperature and under usual fluorescent light from a standard ceiling fitting. We also show that radical-induced reaction of hypervalent iodine reagent plays an important role in the iodo-decarboxylation process. This methodology has a broad scope, providing access to alkyl iodides that are not readily obtainable by existing methods. Investigations to further extend the scope of this reaction and apply it to the synthesis of complex functional molecules are underway in our laboratory.
来源：新浪财经
