Photochemistry of a- Diketones in Carbohydrates: Anomalous Norrish Type II Photoelimination and Norrish- Yang Photocyclization Promoted by the Internal Carbonyl Group

被引：11

作者：

Alvarez-Dorta, Dimitri ^{[1
]}

Leon, Elisa I. ^{[1
]}

Kennedy, Alan R. ^{[2
]}

Martin, Angeles ^{[1
]}

Perez-Martin, Ines ^{[1
]}

Riesco-Fagundo, Concepcion ^{[1
]}

Suarez, Ernesto ^{[1
]}

机构：

[1] CSIC, Inst Prod Nat & Agrobiol, Tenerife 38203, Spain

[2] Univ Strathclyde, WestCHEM Dept Pure & Appl Chem, Glasgow G1 1XL, Lanark, Scotland

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2014年 / 20卷 / 09期

关键词：

carbohydrates; cyclization; diketones; photochemistry; radicals; EFFECT-STEREOSELECTIVITY RELATIONSHIP; ENANTIOSELECTIVE ALDOL ADDITIONS; SOLID-STATE; HYDROGEN ABSTRACTION; GEOMETRIC REQUIREMENTS; COPPER(II) COMPLEXES; ASYMMETRIC INDUCTION; CRYSTAL-STRUCTURE; CHIRAL AUXILIARY; ETHYL PYRUVATE;

D O I：

10.1002/chem.201303843

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

A series of four -diketones placed as 1-pyruvoyl tethers on D-glucopyranose and D-glucopyranosiduronic acid skeletons was prepared in order to determine the influence of captodative and stereoelectronic effects on the regioselectivity of the hydrogen atom transfer (HAT) in Norrish typeII photochemical processes. We observed that the 1,5-HAT regioselectivity can be switched between the two potentially abstractable syn-1,3-diaxial hydrogens at H6 and H8. Highly unusual photoproducts from Norrish typeII photoelimination and Norrish-Yang photocyclization initiated by the excited internal carbonyl group were obtained, in some cases in excellent synthetic yield. The 1,5-HAT transition state in the Norrish typeII photoelimination was investigated by photochemical experiments in the crystalline state.

引用

页码：2663 / 2671

页数：9

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