Externally sensitized mesolytic fragmentations in dithiane-ketone adducts

被引：14

作者：

Gustafson, Tiffany P. ^{[1
]}

Kurchan, Alexei N. ^{[1
]}

Kutateladze, Andrei G. ^{[1
]}

机构：

[1] Univ Denver, Dept Chem & Biochem, Denver, CO 80208 USA

来源：

TETRAHEDRON | 2006年 / 62卷 / 27期

基金：

美国国家科学基金会;

关键词：

D O I：

10.1016/j.tet.2006.03.065

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

The apparent activation enthalpies, Delta H-not equal, for externally sensitized mesolytic fragmentations in benzophenone-dithiane adducts were obtained in variable temperature photolyses and compared with DFT activation barriers calculated for beta-scission in the corresponding oxygen-centered radicals. The results of these experimental and theoretical studies further support the mechanism in which deprotonation of the hydroxy-group, in the transient cation radical, is coupled with intramolecular electron transfer furnishing the O-centered radical, which subsequently fragments. The quantum yields of fragmentation increase for higher alkyl substituted dithiane adducts. (c) 2006 Elsevier Ltd. All rights reserved.

引用

页码：6574 / 6580

页数：7

共 19 条

[1] Efficient electrochemical deprotection of carboxylic and amino acids from their 2-(hydroxymethyl)-1,3-dithiane (Dim) esters [J].

Barnhurst, LA ;

Wan, YQ ;

Kutateladze, AG .

ORGANIC LETTERS, 2000, 2 (06) :799-801

[2] DENSITY-FUNCTIONAL EXCHANGE-ENERGY APPROXIMATION WITH CORRECT ASYMPTOTIC-BEHAVIOR [J].

BECKE, AD .

PHYSICAL REVIEW A, 1988, 38 (06) :3098-3100

[3] PHOTOCHEMICAL DEHYDROFRAGMENTATION REACTIONS - IMPORTANCE OF DONOR AND ACCEPTOR STRUCTURE IN DETERMINATION OF REACTIVITY IN RADICAL ION-PAIRS FORMED IN ELECTRON-TRANSFER PHOTOREACTIONS [J].

CI, XH ;

WHITTEN, DG .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1987, 109 (23) :7215-7217

[4] PHOTOFRAGMENTATION VIA SINGLE-ELECTRON TRANSFER - SELECTIVE LABILIZATION OF C-C BONDS IN AMINO-ALCOHOLS WITH SEVERAL BONDS BETWEEN HETEROATOM SUBSTITUENTS [J].

CI, XO ;

WHITTEN, DG .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1989, 111 (09) :3459-3461

[5]

Frisch M., 2016, Gaussian, V16

[6] Photoinduced electron transfer bond fragmentations [J].

Gaillard, ER ;

Whitten, DG .

ACCOUNTS OF CHEMICAL RESEARCH, 1996, 29 (06) :292-297

[7] ELECTROSYNTHESIS OF 1,2-DITHIOLANE 1-OXIDES FROM SUBSTITUTED 1,3-DITHIANES [J].

GLASS, RS ;

PETSOM, A ;

WILSON, GS ;

MARTINEZ, R ;

JUARISTI, E .

JOURNAL OF ORGANIC CHEMISTRY, 1986, 51 (23) :4337-4342

[8] PHOTOINDUCED REARRANGEMENT OF CARBOCYCLIC 2-PHENYLTHIO-1,3-DIOLS TO DEOXYSUGARS [J].

GRAVEL, D ;

FARMER, L ;

DENIS, RC ;

SCHULTZ, E .

TETRAHEDRON LETTERS, 1994, 35 (48) :8981-8984

[9] PHOTOSENSITIZED CLEAVAGE OF BETA-PHENYLTHIOALCOHOLS - A SYNTHETICALLY USEFUL INDIRECT REDOX CLEAVAGE OF THE OLEFINIC BOND [J].

GRAVEL, D ;

FARMER, L ;

AYOTTE, C .

TETRAHEDRON LETTERS, 1990, 31 (01) :63-66

[10] THE THERMOCHEMISTRY AND REACTIVITY OF ALKOXYL RADICALS [J].

GRAY, P ;

WILLIAMS, A .

CHEMICAL REVIEWS, 1959, 59 (02) :239-328

← 1 2 →