A dichotomy in the enantioselective oxidation of aryl benzyl sulfides: A combined experimental and computational work

被引：6
|
作者：
Capozzi, Maria Annunziata M. [2 ]
Bottoni, Andrea [3 ]
Calvaresi, Matteo [3 ]
Cardellicchio, Cosimo [1 ]
机构：
[1] Univ Bari, CNR ICCOM Dipartimento Chim, Via Orabona 4, I-70125 Bari, Italy
[2] Univ Bari, Dipartimento Chim, Via Orabona 4, I-70125 Bari, Italy
[3] Univ Bologna, Alma Mater Studiorum, Dipartimento Chim G Ciamician, Via F Selmi 2, I-40126 Bologna, Italy
来源：
TETRAHEDRON | 2018年 / 74卷 / 16期
关键词：
Titanium; Sulfoxide; DFT computations; Hydrobenzoin; Oxidation mechanism; CHIRAL TITANIUM COMPLEXES; ASYMMETRIC OXIDATION; SULFENATE ANIONS; THERMOCHEMICAL KINETICS; FLUORINE SUBSTITUTION; ACTIVE SULFOXIDES; PHASE-TRANSFER; ARYLATION; ESOMEPRAZOLE; RESOLUTION;
D O I：
10.1016/j.tet.2018.03.005
中图分类号：
O62 [有机化学];
学科分类号：
070303 ; 081704 ;
摘要：
Pentafluorobenzyl pentafluorophenyl sulfide is oxidised with moderate e.e. value and a low yield by the usually highly successful oxidation protocol based upon tert-butyl hydroperoxide (TBHP) in the presence of a titanium/hydrobenzoin complex. This disappointing result resisted until the present work, in which the switch of the oxidation agent (from TBHP to cumene hydroperoxide), suggested by our previous computations, yielded the enantiopure sulfoxide. This valuable chiral compound was obtained in good yields (76%) without resorting to a chromatographic separation. DFT computations uncovered that this favourable reactivity was originated by a stabilizing pi-pi-stacking between the phenyl group of the oxidant and the pentafluorophenyl moiety of the substrate. (C) 2018 Elsevier Ltd. All rights reserved.
引用
收藏
页码：2041 / 2047
页数：7
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