Synthesis of Chiral Spiro[4.5]decadienones via Chirality-Transferring Oxidative Intramolecular Cyclization of Allenylsilane-Tethered Phenols

Kishimoto, Ryoma; Iwakiri, Yuka; Sakaguchi, Kazuhiko; Nishimura, Takahiro

doi:10.1055/a-2075-3258

Synthesis

2023

DOI: 10.1055/a-2075-3258

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Synthesis of Chiral Spiro[4.5]decadienones via Chirality-Transferring Oxidative Intramolecular Cyclization of Allenylsilane-Tethered Phenols

Ryoma Kishimoto¹,

Yuka Iwakiri²,

Kazuhiko Sakaguchi³

et al.

Abstract: The reaction of phenols having a methylene-tethered chiral allenylsilane at the para position with hypervalent iodine underwent chirality-transferring oxidative intramolecular cyclization accompanied by the dearomatization of phenol to give spiro[4.5]decadienones with silylethynyl group stereoselectively.

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2024

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Cited by 2 publications

References 59 publications

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Stereoselective Synthesis of 4‐Hydroxy‐1‐Silyl‐1‐Allenylboranes and Access to 2‐Silylethynyl‐1,3‐Diols

El Haj Brahim,

Ishak Dridi,

Abderrahim

et al. 2024

Asian J Org Chem

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The highly stereoselective gem‐silylboration of chiral 2‐substituted 1‐ethynylepoxides is reported herein. The reaction involves first the deprotonation of the epoxides in the acetylenic position followed by transmetallation with Et3SiBpin. The transient silylborane ate‐complexes generated undergo the stereoselective 1,2‐migration of the Et3Si‐group to the sp‐hybridized terminus carbon of the ethynyl‐moiety in a stereospecific anti‐addition. The moisture‐sensitive and thermally unstable 4‐hydroxy‐1‐triethylsilyl‐1‐allenyl(pinacolato)boranes thus obtained react with aldehydes through an SE2’‐mode of addition, affording highly functionalized 2‐triethysilylethynyl‐1,3‐diols with a good diastereoselectivity which is rationalized by a Yamamoto‐Houk type transition state model.

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Stereoselective Synthesis of 4‐Hydroxy‐1‐Silyl‐1‐Allenylboranes and Access to 2‐Silylethynyl‐1,3‐Diols

El Haj Brahim,

Ishak Dridi,

Abderrahim

et al. 2024

Asian J Org Chem

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Synthesis of Tricyclic Fused 6–5–4 Carbocycles via Acid-Promoted Cascade Intramolecular Cyclization of Allenylsilane-Tethered Cyclohexadienones

Iwakiri,

Kishimoto,

Sakaguchi

et al. 2024

Org. Lett.

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The reaction of 2,5-cyclohexadienones with methylene-tethered allenylsilane in the presence of Lewis or Brønsted acids leads to a cascade of intramolecular cyclization, yielding stereoselective tricyclic fused 6−5−4 carbocycles featuring a silyl-methylenecyclobutane ring. This transformation is notable for the diastereoselective asymmetric desymmetrization of prochiral dienones, attributed to the axial chirality of allene.

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Synthesis of Chiral Spiro[4.5]decadienones via Chirality-Transferring Oxidative Intramolecular Cyclization of Allenylsilane-Tethered Phenols

Cited by 2 publications

References 59 publications

Stereoselective Synthesis of 4‐Hydroxy‐1‐Silyl‐1‐Allenylboranes and Access to 2‐Silylethynyl‐1,3‐Diols

Stereoselective Synthesis of 4‐Hydroxy‐1‐Silyl‐1‐Allenylboranes and Access to 2‐Silylethynyl‐1,3‐Diols

Synthesis of Tricyclic Fused 6–5–4 Carbocycles via Acid-Promoted Cascade Intramolecular Cyclization of Allenylsilane-Tethered Cyclohexadienones

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