In:
Angewandte Chemie, Wiley, Vol. 134, No. 20 ( 2022-05-09)
Abstract:
Rosenthal's‐reagent‐mediated intramolecular cyclometallation of α,α‐dialkynyldipyrrin nickel(II) complex and subsequent acid treatment afforded a 1,3‐butadiene‐embedded porphyrin(2.1.2.1), 6 , which served as a reactive diene towards dienophiles such as dimethyl acetylenedicarboxylate (DMAD) and benzyne to give corresponding Diels–Alder adducts. Diels–Alder reaction of 6 and benzdiyne gave adducts 14 , 15 a , and 15 b along with a trace amount of porphyrin(2.1.2.1) barrel 13 . Stepwise routes using 14 or 15 a/15 b as a substrate allowed for the synthesis of 13 as a single stereoisomer. The nanobarrel structure for 13 was revealed by X‐ray diffraction, where its cavity held two chloroform molecules via C−H⋅⋅⋅π interaction. DFT calculations revealed that the electrostatic attraction was dominant with binding energy of 32.8 kcal mol −1 .
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.v134.20
DOI:
10.1002/ange.202201327
Language:
English
Publisher:
Wiley
Publication Date:
2022
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