1,3-Dipolar cycloaddition of 2,6-dichlorobenzonitrile oxide to 2-methyl-N-confused porphyrin. Regio- and stereoselective synthesis and structural characterization of 2-aza-21-carbabacteriochlorin and resolution of 2-aza-21-carbachlorin enantiomers.
The 1,3-dipolar cycloaddition reaction of 2-methyl-N-confused porphyrin with 2,6-dichlorobenzonitrile oxide yielded four isomeric monoadducts of carbachlorin type and one diadduct of carbabacteriochlorin type. Two major carbachlorin products, constituting 82% of the monoadducts, were shown to be structural precursors of the unique 2-aza-21-carbabacteriochlorin. Enantiomers of the most abundant isomer of 2-aza-21-carbachlorin (55% of all carbachlorin products) have been resolved. The crystal structures of 2-aza-21-carbabacteriochlorin and the most abundant isomer of 2-aza-21-carbachlorin were characterized by X-ray diffraction.
Key Laboratory of Theoretical Chemistry and Molecular Simulation of Ministry of Education, School of Chemistry and Chemical Engineering, Hunan University of Science and Technology, Xiangtan, Hunan 411201, China. lixiaofang@iccas.ac.cn
Xiaofang
X
Li
Bin
B
Liu
Xianyong
X
Yu
Pinggui
P
Yi
Rongqiong
R
Yi
Piotr J
PJ
Chmielewski
D002722:Chlorobenzenes / Q000737:chemistry*; D003500:Cyclization; D015394:Molecular Structure; D009570:Nitriles / Q000737:chemistry*; D011166:Porphyrins / Q000138:chemical synthesis / Q000737:chemistry*; D013237:Stereoisomerism
C572714:2,6-dichlorobenzonitrile oxide; C572715:2-aza-21-carbabacteriochlorin; C572716:2-aza-21-carbachlorin; D002722:Chlorobenzenes; D009570:Nitriles; D011166:Porphyrins