Ene di- and trimerization of 1-methyl-2-phenylcyclopropene

Lin, Hung‐Chun; Tsai, Ru-Ting; Wu, Hsiao-Pin; Lee, Hsin‐Yi; Lee, Gon-Ann

doi:10.1016/j.tet.2015.11.024

Cited by 10 publications

(5 citation statements)

References 55 publications

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“…In addition, an electron-withdrawing group (EWG) must be present on the aryl fluoride 16 for the S N Ar reaction to proceed. Aryl cyclopropyl sulfides can also be accessed by the addition of thiophenols 14 to cyclopropenes 18 (Scheme 2) [19–20] or to exo -methylenecyclopropanes 20 (Scheme 2) [21–22]. While these methods give access to highly substituted products, the requirement for a strong base could jeopardize their application in the context of synthesis of complex molecules.…”

Section: Introductionmentioning

confidence: 99%

Synthesis of aryl cyclopropyl sulfides through copper-promoted S-cyclopropylation of thiophenols using cyclopropylboronic acid

Benoit¹,

Fnaiche²,

Gagnon³

2019

Beilstein J. Org. Chem.

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The copper-promoted S-cyclopropylation of thiophenols using cyclopropylboronic acid is reported. The procedure operates under simple conditions to afford the corresponding aryl cyclopropyl sulfides in moderate to excellent yields. The reaction tolerates substitution in ortho-, meta- and para-substitution as well as electron-donating and electron-withdrawing groups. The S-cyclopropylation of a thiophenol was also accomplished using potassium cyclopropyl trifluoroborate.

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Section: Introductionmentioning

confidence: 99%

Synthesis of aryl cyclopropyl sulfides through copper-promoted S-cyclopropylation of thiophenols using cyclopropylboronic acid

Benoit¹,

Fnaiche²,

Gagnon³

2019

Beilstein J. Org. Chem.

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“…Similarly, we succeeded in carrying out reactions between unsymmetrically 1,2-disubstituted cyclopropenes 2n , 2o and PRP ( 1 ). 1-Methyl-2-phenylcyclopropene ( 2n ) and 1-phenyl-2-(trimethylsilyl)cyclopropene ( 2o ) synthesized from reliable precursor 1,1,2-tribromo-2-phenylcyclopropane [ 39 – 40 ] were immediately added to a THF solution of nitrogen ylide 1 at room temperature, resulting in the formation of cycloadducts 5b and 5c in satisfactory yields (74% and 79%, respectively). Finally, we attempted to trap parent cyclopropene ( 2p ) as a cycloadduct with PRP ( 1 ).…”

Section: Resultsmentioning

confidence: 99%

Synthesis of bis-spirocyclic derivatives of 3-azabicyclo[3.1.0]hexane via cyclopropene cycloadditions to the stable azomethine ylide derived from Ruhemann's purple

Filatov¹,

Khoroshilova²,

Larina³

et al. 2022

Beilstein J. Org. Chem.

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A reliable method for the synthesis of bis-spirocyclic derivatives of 3-azabicyclo[3.1.0]hexanes through the 1,3-dipolar cycloaddition (1,3-DC) reactions of cyclopropenes to the stable azomethine ylide – protonated form of Ruhemann's purple (PRP) has been developed. Both 3-substituted and 3,3-disubstituted cyclopropenes reacted with PRP, affording the corresponding bis-spirocyclic 3-azabicyclo[3.1.0]hexane cycloadducts in moderate to good yields with high diastereofacial selectivity. Moreover, several unstable 1,2-disubstituted cyclopropenes were successfully trapped by the stable 1,3-dipole under mild conditions. The mechanism of the cycloaddition reactions of cyclopropenes with PRP has been thoroughly studied using density functional theory (DFT) methods at the M11/cc-pVDZ level of theory. The cycloaddition reactions have been found to be HOMOcyclopropene–LUMOylide controlled while the transition-state energies for the reaction of 3-methyl-3-phenylcyclopropene with PRP are fully consistent with the experimentally observed stereoselectivity.

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“…Cyclopropenes 1a , 1b , 1c , 1o , 1d , 1e , 1f , 1l , 1m , 1g – j , 1k , 1n , 2a , 2b , 2c , 2d , 2e , 2f , 2g – i , 3b , and 3c were prepared according to the literature data. Parent cyclopropene ( 3a ) was obtained according to a literature procedure with slight modifications .…”

Section: Methodsmentioning

confidence: 99%

Stereo- and Regioselective 1,3-Dipolar Cycloaddition of the Stable Ninhydrin-Derived Azomethine Ylide to Cyclopropenes: Trapping of Unstable Cyclopropene Dipolarophiles

et al. 2019

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A stereo- and regioselective 1,3-dipolar cycloaddition of the stable ninhydrin-derived azomethine ylide [2-(3,4-dihydro-2H-pyrrolium-1-yl)-1-oxo-1H-inden-3-olate, DHPO] to differently substituted cyclopropenes has been established. As a result, an efficient synthetic protocol was developed for the preparation of biologically relevant spiro[cyclopropa[a]pyrrolizine-2,2′-indene] derivatives. DHPO has proved to be an effective trap for such highly reactive and unstable substrates as parent cyclopropene, 1-methylcyclopropene, 1-phenylcyclopropene, and 1-halo-2-phenylcyclopropenes. It has also been found that 3-nitro-1,2-diphenylcyclopropene undergoes a nucleophilic substitution reaction in alcohols and thiols to afford 3-alkoxy- and 3-arylthio-substituted 1,2-diphenylcyclopropenes, which can be captured as corresponding 1,3-dipolar cycloadducts in the presence of DHPO. These new approaches provide a straightforward strategy for the synthesis of functionally substituted cyclopropa[a]pyrrolizine derivatives. The factors governing regio- and stereoselectivity have been revealed by means of quantum mechanical calculations (M11 density functional theory), including previously unreported N ylide–H cyclopropene second-orbital interactions. The outcome of this work contributes to the study of 1,3-dipolar cycloaddition, as well as enriches chemistry of cyclopropenes and methods for the construction of polycyclic compounds with cyclopropane fragments.

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Ene di- and trimerization of 1-methyl-2-phenylcyclopropene

Cited by 10 publications

References 55 publications

Synthesis of aryl cyclopropyl sulfides through copper-promoted S-cyclopropylation of thiophenols using cyclopropylboronic acid

Synthesis of aryl cyclopropyl sulfides through copper-promoted S-cyclopropylation of thiophenols using cyclopropylboronic acid

Synthesis of bis-spirocyclic derivatives of 3-azabicyclo[3.1.0]hexane via cyclopropene cycloadditions to the stable azomethine ylide derived from Ruhemann's purple

Stereo- and Regioselective 1,3-Dipolar Cycloaddition of the Stable Ninhydrin-Derived Azomethine Ylide to Cyclopropenes: Trapping of Unstable Cyclopropene Dipolarophiles

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