Synthesis of the cyclobutanone core of solanoeclepin A via intramolecular allene butenolide photocycloadditionElectronic supplementary information (ESI) available: experimental details. See http://www.rsc.org/suppdata/ob/b3/b311415e/

Huê, Bùi Thị Bửu; Dijkink, J.; Kuiper, Sanne; Larson, Kimberly K.; Guziec, Frank S.; Fraanje, Jan; Schenk, H.; Maarseveen, Jan H. van; Hiemstra, Henk

doi:10.1039/b311415e

Cited by 30 publications

(13 citation statements)

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“…The structure was confirmed by Xray analysis. [21] Interestingly, this rather strained β-hydroxy ketone appeared to be quite stable, although its stability in aqueous medium at different pH values was not studied. Compound 25 contains the key structural features of the core of solanoeclepin A.…”

Section: Second Approach: [2+2] Photocycloaddition Of Allene Butenolidesmentioning

confidence: 99%

“…[21] The known butenolide 21 [22] was readily converted into silyl dienolate 22 and then treated with 1-bromo-2,3-butadiene [23] in the presence of silver trifluoroacetate at low temperature to provide the desired photosubstrate 23 in 64 % from 21. We were very pleased with this coupling result as the Jefford coupling procedure [19] was not known for allyl bromides of the allenic type.…”

Section: Second Approach: [2+2] Photocycloaddition Of Allene Butenolidesmentioning

confidence: 99%

“…The structure of 24 was proven by X-ray analysis. [21] The exclusive formation of 24 emphasizes the great preference for fivemembered ring formation in intramolecular [2+2]-photocycloaddition (the so-called rule of five). [24] The selectivity difference with the allene studied by Coates ( Figure 2) [20] may be explained by the fact that five-membered ring formation in the case of 23 leads to an allylic radical intermediate, whereas five-membered ring formation from Coates's substrate gives a much less stable vinyl radical, so that other cyclization modes can compete (see Figure 3).…”

Section: Second Approach: [2+2] Photocycloaddition Of Allene Butenolidesmentioning

confidence: 99%

“…The mixture was filtered through Celite® and the filtrate was concentrated in vacuo. [21] 7a-Hydroxymethyl-8-methyleneoctahydro-1,3a-methanoinden-3-ol (26): To a 1 m solution of LiAlH 4 in THF (6.5 mL, 5 equiv.) at room temp.…”

Section: -(Buta-23-dienyl)-4567-tetrahydro-3h-isobenzofuran-1-onmentioning

confidence: 99%

“…The crystal structure of this compound was published elsewhere. [21] Benzyl Buta-2,3-dienoate (31): [31] Benzyl (triphenylphosphoranylidene)acetate (50.42 g, 123 mmol) was dissolved in CH 2 Cl 2 (400 mL) in a three-necked, round-bottomed flask under nitrogen. The solution was stirred at room temp.…”

Section: -(Buta-23-dienyl)-4567-tetrahydro-3h-isobenzofuran-1-onmentioning

confidence: 99%

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Synthesis of the Tricyclic Core of Solanoeclepin A through Intramolecular [2+2] Photocycloaddition of an Allene Butenolide

et al. 2005

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Studies are reported towards the synthesis of solanoeclepin A (1), the hatching agent of potato cyst nematodes. Two approaches are investigated to access the tricyclic core including the intricate bicyclo[2.1.1]hexanone moiety. The first approach is based on the intramolecular [2+2] photocycloaddition of dioxenone butenolide 10 and is shown to be less practical due to the limited synthetic utility of the photoproduct 11. The second approach uses as the key step the intramolecular [2+2] photocycloaddition reaction of allene butenolide 39. This latter photosubstrate is prepared through silver-mediated coupling of silyloxyfuran 9 and allenic bromide

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Section: Second Approach: [2+2] Photocycloaddition Of Allene Butenolidesmentioning

confidence: 99%

Section: Second Approach: [2+2] Photocycloaddition Of Allene Butenolidesmentioning

confidence: 99%

Section: Second Approach: [2+2] Photocycloaddition Of Allene Butenolidesmentioning

confidence: 99%

Section: -(Buta-23-dienyl)-4567-tetrahydro-3h-isobenzofuran-1-onmentioning

confidence: 99%

Section: -(Buta-23-dienyl)-4567-tetrahydro-3h-isobenzofuran-1-onmentioning

confidence: 99%

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Synthesis of the Tricyclic Core of Solanoeclepin A through Intramolecular [2+2] Photocycloaddition of an Allene Butenolide

et al. 2005

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[2+2] Cycloaddition

2010

Comprehensive Organic Name Reactions and Reagents

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Any process involving the breakage of two π bonds and the formation of two s bonds to form a four‐membered ring structure in general belong to [2+2] cycloaddition. There are various chemical reactions based on [2+2] cycloaddition. The cycloaddition of olefins under photochemical conditions is known as photochemical [2+2] cycloaddition and the reversion of [2+2] cycloaddition under UV irradiation referred to as [2+2] photocycloreversion. The molecules with olefinic structure are found to undergo photochemical [2+2] cycloaddition even in solid states. It has been found that in singlet [2+2] photocycloaddition, the regioselectivity and stereoselectivity are determined by the pericyclic minimum and exciple (or excimer) minimum, and the energy barrier between these two minima. The allenes and ketenes have also been found to undergo [2+2] cycloadditions. Furthermore the study finds that for cyclic olefins, as the size of carbocyclic ring decreases, double bonds are more bent and twisted, therefore, the cyclic olefins undergo the [2+2] cycloaddition thermally.

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Allene in katalytischer asymmetrischer Synthese und Naturstoffsynthese

2012

Angewandte Chemie

280

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Allene – Verbindungen mit zwei benachbarten CC‐Bindungen – bilden die einfachste Klasse unter den Cumulenen. Sie verfügen über außergewöhnliche physikalische und chemische Eigenschaften und sind aussichtsreich für Anwendungen in der modernen organischen Chemie. Hier werden Fortschritte in katalytischen asymmetrischen Synthesen und Naturstoffsynthesen erörtert, die auf wohlbekannten Reaktionen von Allenen beruhen: Propargylierungen, Additionen, Cycloadditionen, Cycloisomerisierungen, Cyclisierungen und weitere Reaktionen können sowohl mit als auch ohne Katalysator(en) gelingen. Durch die vielseitige Reaktivität und Substituierbarkeit, die mögliche Übertragung der Achsenchiralität auf ein Chiralitätszentrum und die steuerbare Selektivität können effiziente Wege zu molekularen Zielverbindungen entworfen werden. In diesem Aufsatz haben wir die wichtigsten Themen anhand von ausgewählten Beispielen aus den Jahren 2003 bis 2011 illustriert.

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Synthesis of the cyclobutanone core of solanoeclepin A via intramolecular allene butenolide photocycloadditionElectronic supplementary information (ESI) available: experimental details. See http://www.rsc.org/suppdata/ob/b3/b311415e/

Abstract: The compact tricyclic substructure of solanoeclepin A containing the cyclobutanone ring was prepared by using as the key step a highly regioselective intramolecular [2 + 2]-photocycloaddition reaction between one of the [small pi]-bonds of an allene and the CC double bond of a butenolide.

Cited by 30 publications

References 15 publications

Synthesis of the Tricyclic Core of Solanoeclepin A through Intramolecular [2+2] Photocycloaddition of an Allene Butenolide

Synthesis of the Tricyclic Core of Solanoeclepin A through Intramolecular [2+2] Photocycloaddition of an Allene Butenolide

[2+2] Cycloaddition

Allene in katalytischer asymmetrischer Synthese und Naturstoffsynthese

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