Novel chemical behaviour of a [2,3] sigmatropic rearrangement product of 2-phenyltetrahydrothiopyranium 1-methylide

Flash thermolysis: multiple sigmatropic rearrangements in ortho-substituted aromatic compounds

Canadian Journal of Chemistry ◽

10.1139/v76-538 ◽

1976 ◽

Vol 54 (23) ◽

pp. 3749-3756 ◽

Cited By ~ 9

Author(s):

Pierre de Champlain ◽

Jean-Louis Luche ◽

Robert A. Marty ◽

Paul de Mayo

Keyword(s):

Benzyl Alcohol ◽

Methyl Ether ◽

Aromatic Compounds ◽

Sigmatropic Rearrangement ◽

Methyl Anthranilate ◽

Rearrangement Product ◽

Sigmatropic Rearrangements

A number of o-disubstituted benzenoid substances on flash thermolysis undergo 1,4-elimination of water or alcohols to yield o-quinonoid derivatives. Those products possessing a pentadienyl hydrogen subsequently undergo a 1,5-sigmatropic rearrangement: in many cases the rearrangement product undergoes yet further transformations, such as addition or hydrolysis, and such reactions have been used for their characterization. Included are: the conversion of N-methyl anthranilate esters to o-aminobenzaldehyde; o-(N-methyl)benzyl alcohol and methyl ether to o-toluidine; o-methoxymethylformanilide to o-tolyl isocyanate; and o-carboxymethylformanilide to o-aminobenzaldehyde.

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ChemInform Abstract: Novel Chemical Behavior of a [2,3] Sigmatropic Rearrangement Product of 2-Phenyltetrahydrothiopyranium 1-Methylide.

ChemInform ◽

10.1002/chin.199848175 ◽

2010 ◽

Vol 29 (48) ◽

pp. no-no

Author(s):

S. DOI ◽

N. SHIRAI ◽

Y. SATO

Keyword(s):

Sigmatropic Rearrangement ◽

Chemical Behavior ◽

Rearrangement Product

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Diastereoselective [2,3]-Sigmatropic Rearrangement of N-Allyl Ammonium Ylides

Synthesis ◽

10.1055/s-0039-1690185 ◽

2019 ◽

Vol 51 (22) ◽

pp. 4183-4197 ◽

Cited By ~ 1

Author(s):

Aleksandra Murre ◽

Kristin Erkman ◽

Sandra Kaabel ◽

Ivar Järving ◽

Tõnis Kanger

Keyword(s):

Sigmatropic Rearrangement ◽

Chiral Auxiliary ◽

Rearrangement Product ◽

Asymmetric Reaction ◽

Starting Compound

A rapid and diastereoselective method was developed for the [2,3]-sigmatropic rearrangement of N-allyl ammonium ylides, affording products in up to 95% isolated yields and up to 97:3 dr; most of the desired products were formed within 1 minute. For the asymmetric reaction, a chiral auxiliary was introduced to the starting compound, affording the rearrangement product with high diastereoselectivities.

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Asymetrical Dimer - allyl-palladiu Complexes II. Data from Infrared Spectra and Chemical Behaviour

Revista de Chimie ◽

10.37358/rc.08.7.1888 ◽

2008 ◽

Vol 59 (7) ◽

Author(s):

Maria Maganu ◽

Filip Chiraleu ◽

Constantin Draghici ◽

Gheorghe Mihai

Keyword(s):

Carbon Monoxide ◽

Nmr Spectroscopy ◽

1H Nmr ◽

Infrared Spectra ◽

Analytical Methods ◽

1H Nmr Spectroscopy ◽

Chemical Behaviour ◽

The Asymmetry ◽

Pd Complexes

The previous data obtained by 1H-NMR spectroscopy established the existence of an asymmetry of the bond between Pd and p-allylic groups, even in the p-allyl-Pd complexes dimers which are considered usually symmetric dimers. The asymmetry of the bond depends by the substitutes of the allylic group. Other analytical methods were investigated for additional proof of the obtained results. Thus, this paper discusses how this asymmetry would be reflected in the infrared spectra and in the reaction of the complexes with carbon monoxide.

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Reaction of 1,4-dibromohexafluoro-2-butene with O- and N-nucleophiles

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19880619 ◽

1988 ◽

Vol 53 (3) ◽

pp. 619-625 ◽

Cited By ~ 1

Author(s):

Ivan Hemer ◽

Věra Moravcová ◽

Václav Dědek

Keyword(s):

Kinetic Study ◽

Sodium Methoxide ◽

Allylic Rearrangement ◽

Rearrangement Product

Reaction of 1,4-dibromohexafluoro-2-butene (I) with sodium methoxide, ethoxide or isopropoxide in the corresponding alcohols proceeds with allylic rearrangement under formation of 3-alkoxy-4-bromohexafluoro-1-butenes II-IV. A kinetic study has proven the SN2’ mechanism for reaction of I with potassium phenoxide leading to 4-bromo-3-phenoxyhexafluoro-1-butene (V). Also the reaction of I with ammonia, affording 3-amino-4-bromo-2,4,4-trifluoro-2-butenenitrile (IX), is compatible with the allylic rearrangement by SN2’ mechanism. On the contrary, reaction of I with diethylamine gave no rearrangement product and, after hydrolysis, afforded N,N-diethyl-4-bromo-2,3,3,4,4-pentafluorobutanamide (XVI) and N,N-diethyl-4-bromo-2,3,4,4-tetrafluoro-2-butenamide (XVII) in the ratio 85:15.

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Copper-Catalyzed Synthesis of Axially Chiral Biaryls with Diaryliodonium Salts as Arylation Reagents

Molecules ◽

10.3390/molecules26113223 ◽

2021 ◽

Vol 26 (11) ◽

pp. 3223

Author(s):

Ji-Wei Zhang ◽

Shao-Hua Xiang ◽

Shaoyu Li ◽

Bin Tan

Keyword(s):

Amino Alcohols ◽

Sigmatropic Rearrangement ◽

Synthetic Route ◽

Mild Conditions ◽

Good Substrate ◽

Diaryliodonium Salts ◽

Axially Chiral

NOBIN and BINAM derivatives harboring biaryl frameworks are recognized as a class of important atropisomers with versatile applications. Here, we present an efficient synthetic route to access such compounds through copper-catalyzed domino arylation of N-arylhydroxylamines or N-arylhydrazines with diaryliodonium salts and [3,3]-sigmatropic rearrangement. This reaction features mild conditions, good substrate compatibility, and excellent efficiency. The practicality of this protocol was further extended by the synthesis of biaryl amino alcohols.

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