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Insertion of [1.1.1]propellane into aromatic disulfides

Bär, R. M.; Heinrich, G.; Nieger, M.; Fuhr, O.; Bräse, S.

Herein we present the synthesis of symmetrically and unsymmetrically substituted 1,3-bissulfanylbicyclo[1.1.1]pentanes from disulfides and [1.1.1 ]propellane. Bicyclo [1.1.1]pentanes (BCPs) recently gained interest as rigid linkers and as bioisosters of parasubstituted benzene and alkyne moieties. The most promising precursor for BCPs is [1.1.1] propellane (1). The available methods to synthesize BCPs are quite limited and many groups contribute to the development of novel methods. The insertion of 1 into disulfide bonds is known, but has never been thoroughly investigated. In this study, we show that an UV initiated radical reaction can be used to synthesize symmetrically and unsymmetrically substituted BCP sulfides by reaction of [1.1.1] propellane (1) with disulfides. Depending on the ratio of 1 to the disulfide, only the BCP product (with up to 98% yield) or a mixture of BCP and [2] staffane can be obtained. The reaction tolerates functional groups such as halogens, alkyl and methoxy groups. The separation of the corresponding BCP and [2] staffane products is challenging but possible by column chromatography and preparative TLC in most cases. ... mehr

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Verlagsausgabe §
DOI: 10.5445/IR/1000095854
Veröffentlicht am 24.06.2019
DOI: 10.3762/bjoc.15.114
Zitationen: 12
Web of Science
Zitationen: 10
Cover der Publikation
Zugehörige Institution(en) am KIT Institut für Nanotechnologie (INT)
Institut für Organische Chemie (IOC)
Institut für Toxikologie und Genetik (ITG)
Karlsruhe Nano Micro Facility (KNMF)
Publikationstyp Zeitschriftenaufsatz
Publikationsjahr 2019
Sprache Englisch
Identifikator ISSN: 1860-5397, 2195-951X
KITopen-ID: 1000095854
HGF-Programm 47.01.01 (POF III, LK 01) Biol.Netzwerke u.Synth.Regulat. ITG+ITC
Erschienen in Beilstein journal of organic chemistry
Verlag Beilstein-Institut
Band 15
Seiten 1172-1180
Vorab online veröffentlicht am 28.05.2019
Schlagwörter bicyclo[1.1.1]pentane, bioisosteres, disulfides, linkers, [1.1.1]propellane, 2018-020-022509 SCXD
Nachgewiesen in Scopus
Web of Science
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