1,3-Difunctionalization of Propargyl Silanes with Concomitant 1,2-Silyl Shift: Synthesis of Allyl Functionalized Vinyl Silanes

1,3-Difunctionalization of Propargyl Silanes with Concomitant 1,2-Silyl Shift: Synthesis of Allyl Functionalized Vinyl Silanes

Terminal alkynes with a silyl group at the propargylic position upon activation with electrophiles such as N-bromosuccinimide undergo (E)-selective 1,2-silyl group migration. Subsequently, an allyl cation is formed that is intercepted by an external nucleophile. This approach provides allyl ethers a...

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Veröffentlicht in:Organic letters 2023-06, Vol.25 (25), p.4627-4631
Hauptverfasser: Beļaunieks, Rūdolfs, Puriņš, Mikus, Līpiņa, Rebeka Anna, Mishnev, Anatoly, Turks, Māris
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Sprache:eng
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Alkenes
Catalysis
Ethers
Silanes
Vinyl Compounds
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container_end_page 4631
container_issue 25
container_start_page 4627
container_title Organic letters
container_volume 25
creator Beļaunieks, Rūdolfs
Puriņš, Mikus
Līpiņa, Rebeka Anna
Mishnev, Anatoly
Turks, Māris
description Terminal alkynes with a silyl group at the propargylic position upon activation with electrophiles such as N-bromosuccinimide undergo (E)-selective 1,2-silyl group migration. Subsequently, an allyl cation is formed that is intercepted by an external nucleophile. This approach provides allyl ethers and esters with stereochemically defined vinyl halide and silane handles for further functionalization. The scope of propargyl silanes and electrophile–nucleophile pairs are investigated, and various trisubstituted olefins are prepared in up to 78% yield. The obtained products have been demonstrated to serve as building blocks for transition-metal-catalyzed cross-couplings of vinyl halides, silicon-halogen exchange, and allyl acetate functionalization reactions.
doi_str_mv 10.1021/acs.orglett.3c01245
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subjects Alkenes
Catalysis
Ethers
Silanes
Vinyl Compounds
title 1,3-Difunctionalization of Propargyl Silanes with Concomitant 1,2-Silyl Shift: Synthesis of Allyl Functionalized Vinyl Silanes
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