Photochemical Conversion of Methoxyketene Intermediate into Methyl Ester in the Photolysis of 2-Methoxy-3-dijphenylmethyl-4-diphenylmethylene-2-cyclobuten-1-one

Toda, Fumio; Todo, Y.; Todo, Eishiro

doi:10.1246/bcsj.49.2645

Cited by 14 publications

(4 citation statements)

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“…When the cyclization of allenic carboxylic acid esters to halogenated lactones by addition of bromine was discovered in the mid‐seventies, it was demonstrated soon after that oxaphospholenes could be synthesized from the corresponding allenylphosphonates . Thanks to the discovery by Mark and Boisselle in 1962 of the [2,3]‐sigmatropic rearrangement which occurs after treatment of propargylic alcohols 86 with diethyl chlorophosphites, a very convenient synthesis of allenylphosphonate precursors 87 was available.…”

Section: Synthetic Routes Towards Oxaphospholenes and Benzoxaphospholmentioning

confidence: 99%

Fifty Years of (Benz)oxaphospholene Chemistry

Berton

Heugebaert

Virieux

et al. 2017

Chemistry A European J

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The first synthesis of benzoxaphospholenes dates back to the 1960s. Since then,t he structuralv ariety of reported (benz)oxaphospholenesh as steadily increased. Organophosphorusc ompounds have caught the interesto fs ynthetic chemists for ac ouple of decades now because of their interesting biological properties. Oxaphospholenes,i n particular,c ould serve as carbohydrate mimetics, and benzoxaphospholenes have been reported to possess bactericidal, insecticidal, herbicidal, and fungistatical properties. Transesterification reactions and addition of phosphorus nucleophiles to carbonylc ompoundsw ere reaction types that led to the production of the first (benz)oxaphospholenes.When it was discovered that allenylphosphonates could easily be obtainedf rom propargyl alcohols and dialkylh alophosphites, the electrophile-induced cyclization reaction of these allenylphosphonate precursors resulted in ah uge boom in the amounto fr eports on oxaphospholene synthesis. To this day,t his methodi ss till frequently used. Ring-closing metathesis and Horner-Wadsworth-Emmons reactions have also provent heir potentialf or the preparation of oxaphospholenes. In recent years, Pd, Rh and Au-catalysis have made their entry,g enerating (benz)oxaphospholenes from a wide variety of simple substrates. Ac ouple of miscellaneous methods are summarized at the end of the Review.[a] J.

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Section: Synthetic Routes Towards Oxaphospholenes and Benzoxaphospholmentioning

confidence: 99%

Fifty Years of (Benz)oxaphospholene Chemistry

Berton

Heugebaert

Virieux

et al. 2017

Chemistry A European J

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“…Later, the same group demonstrated that, upon ring‐opening, the allene–ketene intermediate 82 could undergo a rapid [2+2] cycloaddition with benzophenone to afford an oxetanone intermediate, which eventually led to product 83 after a concomitant elimination of diphenylketene 84 (Scheme ) . A similar transformation was realized under an oxygen atmosphere with elimination of carbon dioxide, albeit with a lower yield.…”

Section: Photolysis‐induced Ring Openingmentioning

confidence: 99%

“…(Scheme28). [36] As imilart ransformation was realized under an oxygen atmospherew ith elimination of carbon dioxide,a lbeit with alower yield. In 1984, Schiess et al reported the cycloaddition of benzocyclobutenone 85 (Scheme 29) with variousd ienophiles under flash photolysis conditions.…”

Section: Photolysis-induced Ring Openingmentioning

confidence: 99%

Cyclobutenones and Benzocyclobutenones: Versatile Synthons in Organic Synthesis

Chen

Dong

2016

Chemistry A European J

121

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Cyclobutenones, four-membered ketones bearing an unsaturated carbon–carbon double bond, and their structural sibling benzocyclobutenones, possess unique reactivity. Owing to their inherent high ring strain, such structures readily undergo ring opening under a variety of conditions, including thermolysis, photolysis, and transition metal catalysis, to afford reactive intermediates that can be trapped with nucleophiles, dienophiles, and unsaturated bonds. Their electron-deficient enone moieties are good electrophiles for facile nucleophilic addition. Such properties render cyclobutenones versatile synthons, serving as excellent coupling partners in a vast array of synthetically valuable transformations.

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“…The photolysis of methylenecyclobutenone in the presence of benzophenone or oxygen afforded an a-allenic ester resulting from the cycloaddition reaction of the methoxyketene intermediate (Scheme 23). 49 Scheme 23…”

Section: From Methylenecyclobutanonementioning

confidence: 99%