2021
DOI: 10.1021/acs.orglett.1c01381
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Reactivity of Stabilized Vinyldiazo Compounds toward Alkenyl- and Alkynylsilanes under Gold Catalysis: Regio- and Stereoselective Synthesis of Skipped Dienes and Enynes

Abstract: We report the gold-catalyzed reaction of vinyldiazo compounds and alkenylsilanes to produce skipped dienes, which are common structural motifs in an array of bioactive compounds. This carbon–carbon bond-forming transformation proceeds with complete regio- and stereoselectivity with the silyl group serving as a regio- and stereocontrolling element. Likewise, the use of alkynylsilanes as reaction partners yielded skipped enynes resulting from a C(sp)–C(sp 3 ) coupling. Mechanistic experime… Show more

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Cited by 12 publications
(7 citation statements)
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“…Inspired by Hashmi's elegant work and as part of our on‐going interest in the reactivity of gold vinylcarbene precursors toward unsaturated organosilicon reagents, [9] we became interested in exploring the behavior of propargyl esters toward alkynylsilanes under gold catalysis. We hypothesized that the bulkiness of the silyl group in the alkynylsilane, which might hinder a cyclization reaction, together with the ability of the C‐Si σ‐bond to stabilize an adjacent carbocation (the so‐called β‐silicon effect), [10] could provide a favorable scenario for alternative pathways.…”
mentioning
confidence: 99%
“…Inspired by Hashmi's elegant work and as part of our on‐going interest in the reactivity of gold vinylcarbene precursors toward unsaturated organosilicon reagents, [9] we became interested in exploring the behavior of propargyl esters toward alkynylsilanes under gold catalysis. We hypothesized that the bulkiness of the silyl group in the alkynylsilane, which might hinder a cyclization reaction, together with the ability of the C‐Si σ‐bond to stabilize an adjacent carbocation (the so‐called β‐silicon effect), [10] could provide a favorable scenario for alternative pathways.…”
mentioning
confidence: 99%
“…Additionally, the major formation of the acyclic product 4 when cyclopentanone‐derived silyl enol ether 2 k was used can also confirm the preference for oxonium intermediates B’ (Scheme 6 ) Thus, silyl oxonium intermediate B ’ can evolve to the [4+2] cycloaddition product 3 , or through an alternative pathway, involving silyldeauration, [24] leading to vinyl silane E that in the work up conditions would undergo protodesilylation and double bond isomerization to give the acyclic cyclopentanone derivative 4 .…”
Section: Resultsmentioning
confidence: 82%
“…More recently, while exploring the reactivity of vinyldiazo compounds towards vinylsilanes under gold catalysis (see Section 2.1, Scheme 8), 17 we evaluated alkynylsilanes as reaction partners.…”
Section: Gold-catalyzed Reactions Of Vinyldiazo Compounds With Alkynesmentioning
confidence: 99%