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1.
Chem Asian J ; 16(7): 743-747, 2021 Apr 01.
Article in English | MEDLINE | ID: mdl-33624937

ABSTRACT

A facile synthetic strategy towards conformationally stable chiral chromophores based on dimeric porphyrinoids has been established. A peculiar class of face-to-face intramolecularly interlocked corrole dimers were formed by the oxidative C-C coupling linked at the inner carbon sites upon simple treatment of copper(II) ions. Their intrinsic electronic structures were modulated by the peripheral corrole ring annulations, which lead to distinct optical properties and redox profiles. The stereogenic carbon centers implemented in the confused corrole skeleton provided a rationale for designing novel chiral materials.

2.
Angew Chem Int Ed Engl ; 55(9): 3063-7, 2016 Feb 24.
Article in English | MEDLINE | ID: mdl-26822959

ABSTRACT

Three kinds of fused porphyrinoids, L2-L4, possessing different types of corrole-based frameworks were synthesized from a pyrrole-substituted corrole isomer (norrole L1). Oxidation of L1 afforded a unique N-Cmeso -fused pyrrolyl isonorrole L2, involving the fusion of an auxiliary pyrrolic NH moiety with a meso-sp(3) -hybridized carbon atom. Subsequently, L2 underwent macrocycle transformations to give singly and doubly N-CAr -fused N-confused corroles, L3 and L4, respectively. L3 and L4 contain fused [5.7.6.5]-tetra- and [5.6.7.7.6.5]-hexacyclic structures, respectively, prepared through lateral annulation. These skeletal transformation reactions from norrole to its isomer isonorrole and finally to N-confused corrole indicate that multiply fused porphyrinoids could be readily synthesized from pyrrole-appended confused porphyrinoids.

3.
Org Lett ; 16(24): 6354-7, 2014 Dec 19.
Article in English | MEDLINE | ID: mdl-25483884

ABSTRACT

A C6F5-substituted hexapyrrane (1) was synthesized in one step. Oxidative cyclization of 1 with DDQ afforded a phlorin-dipyrrin conjugate (2), and subsequent FeCl3-assisted oxidative cleavage of 2 afforded a terminally di-α-methoxy substituted hexapyrrin (3). On the other hand, oxidation of 1 with FeCl3 afforded 3, a hexapyrrinone Fe(3+) complex (4), and a hexaphyrin (1,1,1,1,1,0) (5). These results indicate that the oxidation of hexapyrranes may be developed as an effective approach for the syntheses of novel linear and macrocyclic hexapyrroles.


Subject(s)
Coordination Complexes/chemistry , Coordination Complexes/chemical synthesis , Macrocyclic Compounds/chemical synthesis , Pyrroles/chemical synthesis , Catalysis , Cyclization , Macrocyclic Compounds/chemistry , Molecular Structure , Oxidation-Reduction , Pyrroles/chemistry
4.
Angew Chem Int Ed Engl ; 53(51): 14069-73, 2014 Dec 15.
Article in English | MEDLINE | ID: mdl-25323992

ABSTRACT

The first neo-confused hexaphyrin(1.1.1.1.1.0) was synthesized by oxidative ring closure of a hexapyrrane bearing two terminal "confused" pyrroles. The new compound displays a folded conformation with a short interpyrrolic C⋅⋅⋅N distance of 3.102 Å, and thus it readily underwent ring fusion to afford a neo-fused hexaphyrin with an unprecedented 5,5,5,7-tetracyclic ring structure. Furthermore, coordination of Cu(II) triggered a ring opening/contracting reaction to afford a Cu(II) complex of an N-linked pentaphyrin derivative. The roles of reactive N-C bonds in the porphyrinoid macrocycles were demonstrated.


Subject(s)
Porphyrins/chemical synthesis , Molecular Structure , Oxidation-Reduction , Porphyrins/chemistry
5.
J Am Chem Soc ; 135(51): 19119-22, 2013 Dec 26.
Article in English | MEDLINE | ID: mdl-24313813

ABSTRACT

Cyclization of a pentapyrrane with two terminal ß-linked pyrroles afforded a dihydrosapphyrin isomer (1) with the pyrroles linked in a unique ß,α-α,ß mode, which was rather reactive, and thus it readily underwent a ring-contracted rearrangement to a pyrrolyl norrole (2), and succeeding ring expansion to a terpyrrole-containing isosmaragdyrin analogue (4). 1, 2, and 4 contain the internal ring pathways with a minimum of 17, 15, and 16 atoms, respectively. 1, 2, and 4 are almost nonfluorescent, whereas the complex of 2 with Zn(2+) shows a distinct NIR emission peak at 741 nm. The unprecedented pyrrole transformation chemistry by confusion approach is illustrated.

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