Efficient Synthesis of Multiply Seven‐Membered‐Ring Fused Porphyrins by Rhodium‐Catalyzed [5+2] Annulation. (23rd August 2022)

• Record Type: Journal Article
• Authors: Shu, Hui; Guo, Mengjie; Wang, Machongyang; Zhou, Mingbo; Zhou, Bixiang; Xu, Ling; Rao, Yutao; Yin, Bangshao; Osuka, Atsuhiro; Song, Jianxin
• Is Part Of: Angewandte Chemie. Volume 134:Number 39(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-08-23
• Subjects: Alkynes -- Aromaticity -- Fused Porphyrins -- Seven-Membered Rings -- [5+2] Annulation; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202209594
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: Rhodium‐catalyzed reaction of meso‐pyrrol‐2‐yl Ni II porphyrins with internal alkynes proceeded smoothly to give singly, doubly, and quadruply seven‐membered‐ring fused Ni II porphyrins as the first example of [5+2] annulation reaction for porphyrin substrates, where the meso‐appended pyrrole unit serves as a directing group. These reactions are operationally quite simple and easy. A plausible reaction mechanism was proposed on the basis of the isolation of a key intermediate. The structures of the representative products have been revealed to be considerably bent owing to the implemented seven‐membered rings. Doubly fused Zn II and Ni II porphyrins possessing an unsubstituted meso‐position were dimerized to meso‐meso linked dimers by aerobic oxidation with Zn(OAc)2 ⋅2 H2 O and electrochemical oxidation, respectively. The optical and electrochemical highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gaps, as well as the aromatic characters of the fused porphyrins decrease as the fusion parts increases. Abstract : A rhodium‐catalyzed tandem C−H functionalization/annulation of porphyrins with internal alkynes gives singly, doubly, and quadruply seven‐membered‐ring fused porphyrins. This is the first example of [5+2] annulation reaction for porphyrins. The optical and electrochemical highest occupied molecular orbital (HOMO)–lowest unoccupied molecular orbital (LUMO) gaps, as well as the aromatic character of the fused porphyrins decrease as the number of fused parts increases.