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

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

 and *
Received: 29 April 2011; in revised form: 30 May 2011 / Accepted: 31 May 2011 / Published: 7 June 2011
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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 which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

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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.

AMA 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(6):4695-4718.

Chicago/Turabian Style

Golkowski, Martin; Ziegler, Thomas. 2011. "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 16, no. 6: 4695-4718.


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