Silyl Chloroalkenyl and Alkynyl Sulfur Pentafluorides as Versatile Reagents to Access Fundamental SF5 Building Blocks
5 affiliations
- 1Karlsruhe Institute of Technology (KIT) , , Kaiserstrasse 12 , ,
- 2Karlsruhe Institute of Technology
- 3University of Zurich
- 4University of Zurich , , Winterthurerstrasse 190 , ,
- 5Karlsruhe Institute of Technology (KIT) , , Engesserstrasse 15 , ,
Abstract
Herein, we report a second-generation SF5-alkenyl platform reagent granting facile benchtop access to a variety of known and unknown SF5-containing building blocks under mild conditions without any necessity to use pentafluorosulfanylation reagents, such as SF5Cl, on-site. This work overcomes the previous synthetic bottleneck that had prevented a broader use of the triisopropylsilylalkynyl (TASP) reagent. This versatile platform reagent is thermally stable, easy to handle, shows high shelf stability, and can be accessed on a multigram scale. This class of reagents undergoes protodesilylation/nucleophilic substitution reactions with O-, S-, and N-nucleophiles allowing access to (E)-configured α-SF5-enamines (up to >99%), (E)-configured α-SF5-vinyl ethers (up to 90%), another synthetically useful access to (E)-configured β-vinyl sulfides (up to 99%), O,O-acetals (up to 95%), and S,S-acetals (up to 97%) in a single reaction step. Further processing allowed access to S,S-ketene acetals (up to 97%), the corresponding α-SF5-acetic acid esters (up to 88%), as well as α-SF5-acetic acid (92%). Based on these findings, we shed light on the operating reaction mechanism by DFT studies, revealing that the amount of charge accumulated on the α-SF5 carbon controls the efficacy of the reaction with different nucleophiles. In a second part, we reconnected to previous inaccessible alkynyl sulfur pentafluorides by developing a novel in situ elimination strategy and identified the TBDMS derivative as an accessible, stable, and reactive reagent to prepare the complementary (Z)-configured β-vinyl sulfides (up to 85%) in a single reaction step, whereas the pure TMS and TES alkynyl derivatives were found to be inaccessible or unstable under ambient conditions. This report offers a versatile and robust protocol to access important SF5-containing organic motifs employing a commercially available prefunctionalized SF5 reagent.
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BibTeX
@article{bohn2026silyl,
title = {{Silyl Chloroalkenyl and Alkynyl Sulfur Pentafluorides as Versatile Reagents to Access Fundamental SF5 Building Blocks}},
author = {Philipp Bohn and Richard Kraus and Lujie Xu and Sharon Pinus and Max Flügge and André Bütikofer and Silke Wolf and David Rombach},
journal = {ACS Organic \& Inorganic Au},
year = {2026},
month = oct,
doi = {10.1021/acsorginorgau.6c00084},
url = {https://doi.org/10.1021/acsorginorgau.6c00084},
note = {CC BY},
}
RIS
TY - JOUR
TI - Silyl Chloroalkenyl and Alkynyl Sulfur Pentafluorides as Versatile Reagents to Access Fundamental SF5 Building Blocks
AU - Philipp Bohn
AU - Richard Kraus
AU - Lujie Xu
AU - Sharon Pinus
AU - Max Flügge
AU - André Bütikofer
AU - Silke Wolf
AU - David Rombach
PY - 2026
DA - 2026/10/13
JO - ACS Organic & Inorganic Au
DO - 10.1021/acsorginorgau.6c00084
UR - https://doi.org/10.1021/acsorginorgau.6c00084
AB - Herein, we report a second-generation SF5-alkenyl platform reagent granting facile benchtop access to a variety of known and unknown SF5-containing building blocks under mild conditions without any necessity to use pentafluorosulfanylation reagents, such as SF5Cl, on-site. This work overcomes the previous synthetic bottleneck that had prevented a broader use of the triisopropylsilylalkynyl (TASP) reagent. This versatile platform reagent is thermally stable, easy to handle, shows high shelf stability, and can be accessed on a multigram scale. This class of reagents undergoes protodesilylation/nucleophilic substitution reactions with O-, S-, and N-nucleophiles allowing access to (E)-configured α-SF5-enamines (up to >99%), (E)-configured α-SF5-vinyl ethers (up to 90%), another synthetically useful access to (E)-configured β-vinyl sulfides (up to 99%), O,O-acetals (up to 95%), and S,S-acetals (up to 97%) in a single reaction step. Further processing allowed access to S,S-ketene acetals (up to 97%), the corresponding α-SF5-acetic acid esters (up to 88%), as well as α-SF5-acetic acid (92%). Based on these findings, we shed light on the operating reaction mechanism by DFT studies, revealing that the amount of charge accumulated on the α-SF5 carbon controls the efficacy of the reaction with different nucleophiles. In a second part, we reconnected to previous inaccessible alkynyl sulfur pentafluorides by developing a novel in situ elimination strategy and identified the TBDMS derivative as an accessible, stable, and reactive reagent to prepare the complementary (Z)-configured β-vinyl sulfides (up to 85%) in a single reaction step, whereas the pure TMS and TES alkynyl derivatives were found to be inaccessible or unstable under ambient conditions. This report offers a versatile and robust protocol to access important SF5-containing organic motifs employing a commercially available prefunctionalized SF5 reagent.
SN - 2694-247X
ER -