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Molecules 2011, 16(6), 4695-4718; doi:10.3390/molecules16064695

The 2-(Triphenylsilyl)ethoxycarbonyl-(“Tpseoc”-) Group: A New Silicon-Based, Fluoride Cleavable Oxycarbonyl Protecting Group Highly Orthogonal to the Boc-, Fmoc- and Cbz-Groups

Institute of Organic Chemistry, University of Tübingen, Auf der Morgenstelle 18, 72076 Tübingen, Germany
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Author to whom correspondence should be addressed.
Received: 29 April 2011 / Revised: 30 May 2011 / Accepted: 31 May 2011 / Published: 7 June 2011
(This article belongs to the Section Organic Synthesis)
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Abstract

Starting from 2-(triphenylsilyl)ethanol a new oxycarbonyl protecting group cleavable by fluoride ion induced Peterson-elimination has been developed. Known 2-(triphenylsilyl)ethanol has been prepared from commercially available triphenylvinyl-silane by a hydroboration-oxidation sequence using the sterically hindered borane reagent 9-BBN. The silyl alcohol was subsequently transformed into its chloroformate, imidazolylcarboxylic acid ester and p-nitrophenyl carbonate and used in standard protocols for the formation of carbamates and carbonates. The Tpseoc group proved to be highly resistant against acidic conditions applied in removal of tert-butyl esters and the t-Boc-group. It also withstood catalytic hydrogenation, treatment with morpholine, methylhydrazine and Pd-reagents/allyl-scavanger combinations, conditions required to cleave Cbz-, Fmoc-, phthalimide- and Alloc-groups. The Tpseoc-group is cleaved upon treatment with TBAF/CsF at 0 °C or r.t. with cleavage times reaching from < 10 min. to 24 h. Its orthogonality, ease of cleavage and UV-detectability makes the Tpseoc-group a promising alternative to other widely used silicon based amine protecting groups like the Teoc- and SES-groups.
Keywords: Peterson-elimination; protecting group; silicon; fluoride ion; acid stable Peterson-elimination; protecting group; silicon; fluoride ion; acid stable
This is an open access article distributed under the Creative Commons Attribution License (CC BY 3.0).

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MDPI and ACS Style

Golkowski, M.; Ziegler, T. The 2-(Triphenylsilyl)ethoxycarbonyl-(“Tpseoc”-) Group: A New Silicon-Based, Fluoride Cleavable Oxycarbonyl Protecting Group Highly Orthogonal to the Boc-, Fmoc- and Cbz-Groups. Molecules 2011, 16, 4695-4718.

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