Diastereoselectivity control in photosensitized addition of methanol to (R)-(+)-limonene.
Highly diastereodifferentiating bimolecular asymmetric photoreaction was achieved in the photosensitized polar addition of methanol to (R)-(+)-limonene. The diastereomeric excess (de) of the photoadduct could be controlled and fine-tuned by changing the internal/external factors such as solvent polarity, reaction temperature, and structure of the sensitizers. The de increased from 23% obtained upon xylene photosensitization in pure methanol at room temperature to >96% upon singlet sensitization with methyl benzoate at -75 degrees C in 0.5 M methanol/diethyl ether solution.
Shim
Sang Chul
SC
Center for Molecular Design and Synthesis, Department of Chemistry and School of Molecular Science (BK-21), Korea Advanced Institute of Science and Technology (KAIST), 373-1 Guseong-Dong, Yuseong-Gu, Daejeon 305-701, Korea. inoue@chem.eng.osaka-u.ac.jp
Kim
Dong Suk
DS
Yoo
Dong Jin
DJ
Wada
Takehiko
T
Inoue
Yoshihisa
Y
D053138:Cyclohexenes; D004986:Ether; D000077222:Limonene; D000432:Methanol; D008958:Models, Molecular; D008968:Molecular Conformation; D010777:Photochemistry; D012996:Solutions; D013050:Spectrometry, Fluorescence; D013237:Stereoisomerism; D013329:Structure-Activity Relationship; D013729:Terpenes
D053138:Cyclohexenes; D012996:Solutions; D013729:Terpenes; D004986:Ether; D000077222:Limonene; D000432:Methanol