Phosphorus-Containing Bis-allenes: Synthesis and Heterocyclization Reactions Mediated by Iodine or Copper Dibromide

Essid, Ines; Laborde, Coralie; Legros, Frédéric; Sevrain, Nicolas; Touil, Soufiane; Rolland, Marc; Ayad, Tahar; Volle, J.‐N.; Pirat, Jean‐Luc; Virieux, David

doi:10.1021/acs.orglett.7b00648

Cited by 19 publications

(21 citation statements)

References 49 publications

(18 reference statements)

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“…Thanks to the rotation of the aromatic ring, the o-methyl group could be oriented away from the allene, allowing iodine also in this case to be attacked by the distal allenyl double bond. For such compounds, steric hindrance induces slow rotation of the C o-tolyl −C oxaphospholene bond and rotamers were observed in both 1 H NMR and 13 C NMR. For each epimer, a pair of rotamers is observed at room temperature, due to hindered rotation around the C oxaphospholene −C o-tolyl bond.…”

Section: ■ Results and Discussionmentioning

confidence: 99%

Three-Step Synthesis of Chiral Spirocyclic Oxaphospholenes

et al. 2017

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Chiral spirocylic oxaphospholenes were prepared in a three-step sequence from chiral pool terpenoid ketones. After addition of a metal acetylide, the resulting propargyl alcohols were converted stereoselectively into their allenylphosphonate counterparts. In the last step, they were conveniently cyclized into spirooxaphospholenes with one equivalent of iodine without purification. When starting from sterically hindered terpenes, allenylphosphonates were also easily obtained but showed to be unreactive or rearranged under these cyclization conditions.

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Section: ■ Results and Discussionmentioning

confidence: 99%

Three-Step Synthesis of Chiral Spirocyclic Oxaphospholenes

et al. 2017

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“…[111] These were prepared through aG laser-Hay coupling reaction of the corresponding alkynes 121 and 122,f ollowed by a[ 2,3]sigmatropic rearrangement of the resulting (un)symmetrical dialkynes 123 with diethylc hlorophosphite. [111] These were prepared through aG laser-Hay coupling reaction of the corresponding alkynes 121 and 122,f ollowed by a[ 2,3]sigmatropic rearrangement of the resulting (un)symmetrical dialkynes 123 with diethylc hlorophosphite.…”

Section: Throughcyclization Of Allenylphosphonates Promoted By Electrmentioning

confidence: 99%

“…Very recently,t he group of Virieux reported on the double cyclization of bisallenylphosphonates 124 (Scheme 29). [111] These were prepared through aG laser-Hay coupling reaction of the corresponding alkynes 121 and 122,f ollowed by a[ 2,3]sigmatropic rearrangement of the resulting (un)symmetrical dialkynes 123 with diethylc hlorophosphite. All derivatives reacted in good to excellent yields in this two-step sequence, except for the cyclopropyl-substituted propargyl alcohol.…”

Section: Scheme26 Halolactonization Of Monoesters Of Allenylphosphonmentioning

confidence: 99%

“…Very recently, the group of Virieux reported on the double cyclization of bisallenylphosphonates 124 (Scheme ) . These were prepared through a Glaser–Hay coupling reaction of the corresponding alkynes 121 and 122 , followed by a [2,3]‐sigmatropic rearrangement of the resulting (un)symmetrical dialkynes 123 with diethyl chlorophosphite.…”

Section: Synthetic Routes Towards Oxaphospholenes and Benzoxaphospholmentioning

confidence: 99%

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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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“…Electrophilic reactions of allenes have been intensely explored in organic synthesis [1–3]. In particular, reports on electrophilic activation of phosphorylallenes are numerous [4–10]. Miscellaneous electrophiles, such as sulfenyl, selenyl, and telluryl chlorides, were used in reactions with these allenes.…”

Section: Introductionmentioning

confidence: 99%

Different reactivity of phosphorylallenes under the action of Brønsted or Lewis acids: a crucial role of involvement of the P=O group in intra- or intermolecular interactions at the formation of cationic intermediates

Lozovskiy¹,

Ivanov²,

Vasilyev³

2019

Beilstein J. Org. Chem.

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3-Methylbuta-1,2-dien-1-ylphosphonic acid derivatives (phosphorylallenes) [X2(O=)P–CR=C=CMe2, X = Cl, OMe, NR2, or SAr] undergo intramolecular cyclization into the corresponding 1,2-oxaphospholium ions in the Brønsted superacid TfOH. These cations have been thoroughly studied by means of NMR spectroscopy. The hydrolysis of superacidic solutions of these species afforded cyclic phosphonic acids and other phosphorus-containing compounds. Contrary to Brønsted acids, 3-methylbuta-1,2-dien-1-ylphosphonic dichloride [Cl2(O=)P–HC=C=CMe2] reacted with the Lewis acid AlCl3 in an intermolecular way forming noncyclic intermediates, which were investigated by NMR spectroscopy and DFT calculations. Hydrolysis of these species resulted in the formation of phosphoryl-substituted allyl alcohols and 1,3-butadienes. A strong coordination of the oxygen of the P=O group with AlCl3 prevented the formation of cyclic 1,2-oxaphospholium ions and played a crucial role in the different reactivity of such phosphorylallenes under the action of Brønsted or Lewis acids. Apart from that, the reaction of dichlorophosphorylallenes with arenes and AlCl3 led to products of hydroarylation of the allene system, phosphoryl-substituted alkenes and/or indanes. This is the first example of a Lewis acid-promoted intermolecular hydroarylation of allenes bearing electron-withdrawing substituents. Plausible reaction mechanisms have been proposed on the basis of the investigated reactions, and NMR analysis and DFT studies of the intermediate cationic species.

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Phosphorus-Containing Bis-allenes: Synthesis and Heterocyclization Reactions Mediated by Iodine or Copper Dibromide

Cited by 19 publications

References 49 publications

Three-Step Synthesis of Chiral Spirocyclic Oxaphospholenes

Three-Step Synthesis of Chiral Spirocyclic Oxaphospholenes

Fifty Years of (Benz)oxaphospholene Chemistry

Different reactivity of phosphorylallenes under the action of Brønsted or Lewis acids: a crucial role of involvement of the P=O group in intra- or intermolecular interactions at the formation of cationic intermediates

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