Intramolecular aromatic 1,5-hydrogen transfer in free radical reactions - III. Reactivity of diaryl ketones, ethers, thioethers, sulfoxydes, and sulfones. An experimental and theoretical study

被引：20

作者：

Karady, S

Cummins, JM

Dannenberg, JJ

del Rio, E

Dormer, PG

Marcune, BF

Reamer, RA

Sordo, TL

机构：

[1] Merck & Co Inc, Merck Res Labs, Proc Res Dept, Rahway, NJ 07065 USA

[2] CUNY Hunter Coll, Dept Chem, New York, NY 10021 USA

[3] CUNY, Grad Sch, New York, NY 10021 USA

[4] Univ Oviedo, Dept Quim Fis & Analit, Oviedo 33006, Principado De A, Spain

来源：

ORGANIC LETTERS | 2003年 / 5卷 / 08期

关键词：

D O I：

10.1021/ol027301t

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Experiments show that free radical hydrogen shift is significant in the Pschorr cyclization of diphenyl ethers (X = O) and thioethers (X = S) and does not take place with sufoxides; (X = SO) and sulfones; (X = SO2). DFT calculations of the product ratios, activation energies, rate constants for H-transfers, and ring-closings at the UB3PW91/6-31G(d,p) level are in excellent agreement with the experimental results reported here and elsewhere in the literature.

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页码：1175 / 1178

页数：4

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