Intramolecular arene epoxidation by phosphadioxiranes.
Singlet oxygen reacts with binaphthyl phosphine derivatives such as 1,1'-binaphthyl di-tert-butyl phosphine to form the corresponding binaphthyl-2-oxide phosphine oxides. This new intramolecular arene epoxidation reaction proceeds with complete retention of stereochemistry. The binaphthyl-2-oxide di-tert-butyl phosphine oxide undergoes a slow "NIH-rearrangement" to form the corresponding hydroxylated product. A transient phosphadioxirane intermediate has been directly observed by low-temperature NMR. Kinetic analyses show that all of the phosphadioxirane intermediate is converted to product. [reaction: see text]
Zhang
Dong
D
Department of Chemistry and Biochemistry, California State University-Los Angeles, Los Angeles, CA 90032, USA.
Gao
Ruomei
R
Afzal
Shabana
S
Vargas
Mario
M
Sharma
Shantanu
S
McCurdy
Alison
A
Yousufuddin
Muhammed
M
Stewart
Timothy
T
Bau
Robert
R
Selke
Matthias
M
D002384:Catalysis; D006576:Heterocyclic Compounds, 4 or More Rings / Q000138:chemical synthesis* / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D015394:Molecular Structure; D009281:Naphthalenes / Q000138:chemical synthesis* / Q000737:chemistry; D010100:Oxygen / Q000737:chemistry; D010720:Phosphines / Q000737:chemistry
D006576:Heterocyclic Compounds, 4 or More Rings; D009281:Naphthalenes; D010720:Phosphines; D010100:Oxygen