A straightforward, visible-light triggered desilylation of arylsilanes by thiyl radicals is presented. Silyl groups are often used to block a reactive position in multi-step organic synthesis, for which a mild cleavage at a late-stage will provide new possibilities and disconnection routes by C -Si cleavage/deprotection. In this work, commercially available and cheap disulfides are employed for the first time in this type of C(sp )-Si bond cleavage reactions. Thus, upon irradiation with visible-light, homolytic cleavage of the disulfide give rise to the corresponding thiyl radical that allows for a radical chain mechanism. This methodology represents a mild, fast and simple approach suitable for a broad variety of simply substituted arylsilanes. Moreover, the procedure could be easily extended to natural products and therapeutic derivatives, showing its robustness and synthetic application potential.
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http://dx.doi.org/10.1002/chem.202203347 | DOI Listing |
Chemistry
February 2023
Organic Chemistry Institute, University of Münster, Corrensstraße 36, 48149, Münster, Germany.
A straightforward, visible-light triggered desilylation of arylsilanes by thiyl radicals is presented. Silyl groups are often used to block a reactive position in multi-step organic synthesis, for which a mild cleavage at a late-stage will provide new possibilities and disconnection routes by C -Si cleavage/deprotection. In this work, commercially available and cheap disulfides are employed for the first time in this type of C(sp )-Si bond cleavage reactions.
View Article and Find Full Text PDFOrg Lett
March 2022
Organic Chemistry Institute, Westfälische Wilhelms University Münster, Corrensstraße 36, 48149 Münster, Germany.
The first visible-light-mediated photocatalytic, metal- and base-free protodesilylation of arylsilanes is presented. The C(sp)-Si bond cleavage process is catalyzed by a 5 mol % loading of a commercially available acridinium salt upon blue-light irradiation. Two simple approaches have been identified employing either aerobic or hydrogen atom transfer cocatalytic conditions, which enable the efficient and selective desilylation of a broad variety of simple and complex arylsilanes under mild conditions.
View Article and Find Full Text PDFOrganometallics
December 2015
School of Chemistry, University of Manchester, Manchester M13 9PL, United Kingdom.
The addition of AlCl to four-coordinate boranes of the general formula (C-N-chelate)BCl results in halide abstraction and formation of three-coordinate borenium cations of the general formula [(C-N-chelate)BCl]. The latter react with both arylstannanes and arylsilanes by boro-destannylation and -desilylation, respectively, to form arylated boranes. Catalytic quantities of AlCl were sufficient to effect high-yielding arylation of (C-N-chelate)BCl.
View Article and Find Full Text PDFJ Org Chem
August 2007
Department of Organic Chemistry, Israel Institute for Biological Research, Ness-Ziona 74100, Israel.
A facile and efficient method for the cleavage of the Ar-Si bond of various aryl trimethyl silanes is described. When adsorbed on montmorillonite KSF (mont KSF), these arylsilanes readily undergo a solvent-free protodesilylation to the corresponding arenes at room temperature in excellent yields. This approach seems to be superior to the traditional mild methods (i.
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