Soft Propargylic Deprotonation: Designed Ligand Enables Au-Catalyzed Isomerization of Alkynes to 1,3-Dienes

By functionalizing the privileged biphenyl-2-ylphosphine with a basic amino group at the rarely explored 3′ position, the derived gold­(I) complex possesses orthogonally positioned “push” and “pull” forces, which enable for the first time soft propargylic deprotonation and permit the bridging of a d...

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Bibliographic Details
Published inJournal of the American Chemical Society Vol. 136; no. 25; pp. 8887 - 8890
Main Authors Wang, Zhixun, Wang, Yanzhao, Zhang, Liming
Format Journal Article
LanguageEnglish
Published WASHINGTON American Chemical Society 25.06.2014
Amer Chemical Soc
Subjects
Alkadienes - chemical synthesis
Alkadienes - chemistry
Alkynes
Alkynes - chemistry
Aniline
Bridging
Catalysis
Chemistry
Chemistry, Multidisciplinary
Communication
dimethyl sulfoxide
gold
Gold - chemistry
hydrogen
Isomerization
Ligands
Molecular Conformation
Physical Sciences
Protons
Science & Technology
Stereoisomerism
TRIETHYLAMINE
PALLADIUM
ACIDITIES
COUPLING REACTIONS
C-N
PHOSPHINES
BOND-FORMING REACTIONS
COMPLEXES
SUZUKI-MIYAURA
ARYL CHLORIDES
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Summary:By functionalizing the privileged biphenyl-2-ylphosphine with a basic amino group at the rarely explored 3′ position, the derived gold­(I) complex possesses orthogonally positioned “push” and “pull” forces, which enable for the first time soft propargylic deprotonation and permit the bridging of a difference of >26 pK a units (in DMSO) between a propargylic hydrogen and a protonated tertiary aniline. The application of this design led to efficient isomerization of alkynes into versatile 1,3-dienes with synthetically useful scope under mild reaction conditions.
Bibliography:NIH RePORTER
ObjectType-Article-1
SourceType-Scholarly Journals-1
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content type line 23
ISSN:0002-7863
1520-5126
1520-5126
DOI:10.1021/ja503909c