Studies on the syntheses of spiro-dienone compounds. VII. Novel synthesis of the spiro[4.5]decane carbon framework.

Iwata, Chuzo; Yamada, Minoru; Shinoo, Yasutaka; Kobayashi, Kazue; Okada, Hideko

doi:10.1248/cpb.28.1932

Cited by 9 publications

(4 citation statements)

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“…(b) Base-Catalyzed 1,3-Hydrogen Shift. Several examples of this type of transformation are described in cycloheptatrienic systems, catalyzed by triethylamine, − 1,8-diazabicyclo[5.4.0]undec-7-ene, , or potassium tert -butoxide. , The mechanism and regioselectivity have been studied for cycloheptatrienes bearing electron-withdrawing groups. − There are also a few examples of thermal, − photochemical, or acid-catalyzed 57,58 1,3-hydrogen shifts. In most cases, the hydrogen atom shifts from a ring-junction position to the nearest unsubstituted position (path A, Scheme ). ,,− ,− In the case where cycloheptatriene 18 has R 1 ≠ H (path B, Scheme ), the 1,3-shift is very unfavored.…”

Section: Resultsmentioning

confidence: 99%

“…46,47 The mechanism and regioselectivity have been studied for cycloheptatrienes bearing electron-withdrawing groups. [48][49][50][51][52] There are also a few examples of thermal, [53][54][55][56][57] photochemical, 58 or acid-catalyzed 57,58 1,3-hydrogen shifts. In most cases, the hydrogen atom shifts from a ring-junction position to the nearest unsubstituted position (path A, Scheme 5).…”

Section: Resultsmentioning

confidence: 99%

“…27,28,[42][43][44][56][57][58] In the case where cycloheptatriene 18 has R 1 * H (path B, Scheme 5), the 1,3-shift is very unfavored. The system evolves toward the spirodienone 21 43,[53][54][55] if an oxygenated substituent is present at R 2 or remains in the less constrained norcaradiene form 20 59 in the other cases.…”

Section: Resultsmentioning

confidence: 99%

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A New Access to Dihydrotropones through Ring Expansion of Spirocyclohexadienones: Synthesis and Mechanism

et al. 2007

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In this paper we report the rearrangement of spirocyclohexadienones into dihydrotropones in basic conditions as a new method for the preparation of seven-membered ring ketones, which are key building blocks for the synthesis of tropoloalkaloids. DFT calculations and deuterium labeling studies support the mechanism we propose for this rearrangement, involving the ring opening of a spirocyclopropane intermediate followed by successive base-catalyzed 1,3-hydrogen shifts. The X-ray structure of the resulting dihydrotropone shows near-perfect planarity and the conjugation gain is likely to be the driving force of the reaction.

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Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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A New Access to Dihydrotropones through Ring Expansion of Spirocyclohexadienones: Synthesis and Mechanism

et al. 2007

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“…[107] Under coppercatalyzed conditions, the Buchner cyclization of diazoketones bearing para-hydroxy phenyl group afforded a mixture of spirodienone and cycloheptatrienone products (Scheme 22). [107,108] Scheme 20. Intramolecular Buchner reaction.…”

Section: Intramolecular Buchner Reactionmentioning

confidence: 99%

Skeletal Editing of (Hetero)Arenes Using Carbenes

Liu

Sivaguru

Ning

et al. 2023

Chemistry A European J

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(Hetero)arenes continue to prove their indispensability in pharmaceuticals, materials science, and synthetic chemistry. As such, the controllable modification of biologically significant (hetero)arenes towards diverse more‐potent complex molecular scaffolds through peripheral and skeletal editing has been considered a challenging goal in synthetic organic chemistry. Despite many excellent reviews on peripheral editing (i. e., C−H functionalization) of (hetero)arenes, their skeletal editings via single atom insertion, deletion, or transmutations have received less attention in the review literature. In this review, we systematically summarize the state‐of‐the‐art skeletal editing reactions of (hetero)arenes using carbenes, with a focus on general mechanistic considerations and their applications in natural product syntheses. The potential opportunities and inherent challenges encountered while developing these strategies are also highlighted.

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ChemInform Abstract: STUDIES ON THE SYNTHESES OF SPIRODIENONE COMPOUNDS. VII. NOVEL SYNTHESIS OF THE SPIRO(4.5)DECANE CARBON FRAMEWORK

Iwata¹,

Yamada²,

Shinoo³

et al. 1980

Chemischer Informationsdienst

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Studies on the syntheses of spiro-dienone compounds. VII. Novel synthesis of the spiro[4.5]decane carbon framework.

Cited by 9 publications

References 1 publication

A New Access to Dihydrotropones through Ring Expansion of Spirocyclohexadienones: Synthesis and Mechanism

A New Access to Dihydrotropones through Ring Expansion of Spirocyclohexadienones: Synthesis and Mechanism

Skeletal Editing of (Hetero)Arenes Using Carbenes

ChemInform Abstract: STUDIES ON THE SYNTHESES OF SPIRODIENONE COMPOUNDS. VII. NOVEL SYNTHESIS OF THE SPIRO(4.5)DECANE CARBON FRAMEWORK

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