1,6‐Methano[10]Annulene

Vogel, Emanuel; Klug, W.; Breuer, A.

doi:10.1002/0471264180.os054.02

Cited by 14 publications

(16 citation statements)

References 11 publications

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“…The construction was by no means trivial (Scheme 4), but Vogel's procedure was powerful enough to render it suitable for inclusion in Organic Syntheses. [45] Naphthalene undergoes a Birch reduction to isotetralin that then undergoes cyclopropanation with dichlorocarbene primarily at the internal olefin. Reductive dehalogenation followed by oxidation with DDQ facilitates ring opening and subsequent aromatization of the annulene ring.…”

Section: A Bigger Benzene: [10]annulenementioning

confidence: 99%

Emerging Prospects for Unusual Aromaticity in Organic Electronic Materials: The Case for Methano[10]annulene

2008

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Section: A Bigger Benzene: [10]annulenementioning

confidence: 99%

Emerging Prospects for Unusual Aromaticity in Organic Electronic Materials: The Case for Methano[10]annulene

2008

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“…It proceeds via single electron and proton transfer steps involving a radical anion transition state; alkali metals dissolved in ammonia serve as electron and an alcohol as the proton donor . Under Birch conditions, 1 is reduced to the non‐conjugated 1,4,5,8‐tetrahydronaphthalene ( 3 ) (Scheme b) . The direct reduction to a conjugated product is not feasible by Birch reduction as such products are susceptible to further reduction.…”

Section: Methodsmentioning

confidence: 99%

Enantioselective Enzymatic Naphthoyl Ring Reduction

Willistein

Haas

Fuchs

et al. 2018

Chemistry A European J

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Birch reductions of aromatic hydrocarbons by means of single-electron-transfer steps depend on alkali metals, ammonia, and cryogenic reaction conditions. In contrast, 2-naphthoyl-coenzyme A (2-NCoA) and 5,6-dihydro-2-NCoA (5,6-DHNCoA) reductases catalyze two two-electron reductions of the naphthoyl-ring system to tetrahydronaphthoyl-CoA at ambient temperature. Using a number of substrate analogues, we provide evidence for a Meisenheimer complex-analogous intermediate during 2-NCoA reduction, whereas the subsequent reduction of 5,6-dihydro-2-NCoA is suggested to proceed via an unprecedented cationic transition state. Using vibrational circular dichroism (VCD) spectroscopy, we demonstrate that both enzymatic reductions are highly stereoselective in D O, providing an enantioselective pathway to products inaccessible by Birch reduction. Moreover, we demonstrate the power of VCD spectroscopy to determine the absolute configuration of isotopically engendered alicyclic stereocenters.

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“…structurally closer related to carba-Serenolide The main difference in the superposition analysis in Figure 5 is the aromatic ring of 32, and since the important difference between an aromatic ring binding motif and their hydrogenated counterparts had just been demonstrated for the family of marine odorants, 20 it was envisaged to investigate next the influence of a partially and fully hydrogenated ring system on the odor. To this aim, the aromatic alcohol 28 was subjected to Birch reduction employing Na in NH 3 and EtOH at -70 °C for 6 h and 12 h at r.t., 21 which afforded the cyclohexa-1,4-dien-1-yl system 29 in 21% yield due to difficulties in isolation. Esterification with cyclopropanecarboxylic acid under Steglich conditions 13 then provided in 90% yield the partially unsaturated system 33, which turned out to be odorless just as 31 and 32.…”

Section: Scheme 3 Synthesis Of Derivatives Of M-isopropenylcumene (25)mentioning

confidence: 99%

“…1 H NMR (400 MHz, CDCl 3 ): δ = 3.32 (s, 2 H, 1-H 2 ), 1.62-1.53 (m, 2 H, 4′-H a , 6′-H a ), 1.46-1. 21…”

Section: Syn Thesismentioning

confidence: 99%

Search for New Linear Musks Devoid of a 2,2-Dimethyl-1,4-dioxabutane Unit: Synthesis and Olfactory Properties of 5-Substituted (3E)-Hex-3-enoates on the Way to Carba-Helvetolide and Carba-Serenolide

Nguyen¹,

Sutter²,

Kraft³

2017

Synthesis

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Since the nucleophilic opening of isobutylene oxide competes with the formation of polyethers, the 2,2-dimethyl-1,4-dioxabutane moiety constitutes the most important cost driver in the synthesis of linear musks. Therefore, musk motifs devoid of this structural element would be highly attractive. Based on molecular modeling considerations, 5-methyl-substituted (3E)-configured alk-3-enoic esters accessible by deconjugative Knoevenagel reaction with malonic acid in the presence of piperidinium acetate with citronellal and Florhydral as substrates, were synthesized but showed disappointing olfactory properties, as did inverted ester motifs or dimethyl carbinols. Moving closer to carba-Serenolide structures, isobutyronitrile was added to m-isopropenylcumene. DIBAL-H with subsequent alanate reduction provided 4-(3-isopropylphenyl)-2,2-dimethylpentan-1-ol, which was either directly esterified, or esterified after Birch reduction and full hydrogenation. While these target structures were all odorless, (2E)-4-(3,3-dimethylcyclohexyl)pent-2-en-1-yl cyclopropanecarboxylate turned out to be a decent musk odorant (4.1 ng/L air). This proved the concept of an (E)-configured double bond in the middle of anticipated horseshoe-shaped conformers, but casted doubt on the non-importance of the ether oxygens in Helvetolide and Serenolide. Therefore, carba-Helvetolide and carba-Serenolide were synthesized from 3,3-dimethylcyclohexanone, and indeed turned out to be completely odorless. So polar interactions play a crucial role in the receptor interaction of these linear musks beyond merely favoring horseshoe-shaped conformers.

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1,6‐Methano[10]Annulene

Abstract: 1,6‐Methano[10]Annulene intermediate: 1,4,5,8‐ Tetrahydronaphthalene ( isotetralin ) intermediate: 11,11‐ Dichlorotricyclo [4.4.1.0 1,6 ] undeca ‐3,8‐ diene … Show more

Cited by 14 publications

References 11 publications

Emerging Prospects for Unusual Aromaticity in Organic Electronic Materials: The Case for Methano[10]annulene

Emerging Prospects for Unusual Aromaticity in Organic Electronic Materials: The Case for Methano[10]annulene

Enantioselective Enzymatic Naphthoyl Ring Reduction

Search for New Linear Musks Devoid of a 2,2-Dimethyl-1,4-dioxabutane Unit: Synthesis and Olfactory Properties of 5-Substituted (3E)-Hex-3-enoates on the Way to Carba-Helvetolide and Carba-Serenolide

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1,6‐Methano[10]Annulene

Abstract: 1,6‐Methano[10]Annulene intermediate: 1,4,5,8‐ Tetrahydronaphthalene ( isotetralin ) intermediate: 11,11‐ Dichlorotricyclo [4.4.1.0 1,6 ] undeca ‐3,8‐ diene … Show more

Cited by 14 publications

References 11 publications

Emerging Prospects for Unusual Aromaticity in Organic Electronic Materials: The Case for Methano[10]annulene

Emerging Prospects for Unusual Aromaticity in Organic Electronic Materials: The Case for Methano[10]annulene

Enantioselective Enzymatic Naphthoyl Ring Reduction

Search for New Linear Musks Devoid of a 2,2-Dimethyl-1,4-dioxa­butane Unit: Synthesis and Olfactory Properties of 5-Substituted (3E)-Hex-3-enoates on the Way to Carba-Helvetolide and Carba-Serenolide

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Search for New Linear Musks Devoid of a 2,2-Dimethyl-1,4-dioxabutane Unit: Synthesis and Olfactory Properties of 5-Substituted (3E)-Hex-3-enoates on the Way to Carba-Helvetolide and Carba-Serenolide