Synthesis of Subporphyrin Free Bases

Le Liu; Jinseok Kim; Ling Xu; Yutao Rao; Mingbo Zhou; Bangshao Yin; Juwon Oh; Dongho Kim; Atsuhiro Osuka; Jianxin Song

doi:10.1002/anie.202214342

Synthesis of Subporphyrin Free Bases

Le Liu, Jinseok Kim, Ling Xu, Yutao Rao, Mingbo Zhou, Bangshao Yin, Juwon Oh, Dongho Kim, Atsuhiro Osuka, Jianxin Song

Department of Chemistry

Research output: Contribution to journal › Article › peer-review

1 Citation (Scopus)

Abstract

B^III subporphyrins are the legitimate ring-contracted porphyrins consisting of three pyrroles and three meso-carbons and their chemistry has been extensively developed since the first synthesis in 2006. However, subporphyrin free bases have never been synthesized, despite tremendous attempts to remove the B^III ion. Here we report that Suzuki–Miyaura coupling between α,α′-diborylated tripyrrane 1 and tetrabromide 5 gave subporphyrin free bases 6, 6 A, and free base dimer 7 in 6 %, 4 %, and 2 % yields as the first examples. Subporphyrin free bases exhibit curved bowl-like structures and distinct 14π-aromaticity. Steady-state and time-resolved spectroscopy revealed that the excited-state behaviors of the subporphyrin free bases are comparable with those of the corresponding B^III subporphyrins. Rotational relaxation processes in the excited states have been revealed, which enhance the electronic interactions with the meso-aryl substituents and between the two subporphyrins.

Original language	English
Article number	e202214342
Journal	Angewandte Chemie - International Edition
Volume	61
Issue number	50
DOIs	https://doi.org/10.1002/anie.202214342
Publication status	Published - 2022 Dec 12

Bibliographical note

Funding Information:
The work is supported by the National Natural Science Foundation of China (Grant Nos. 22071052, 21772036, 21702057, 21602058), Science and Technology Planning Project of Hunan Province (2018TP1017), Science and Technology Innovation Program of Hunan Province (2021RC4059). The work is also supported by a National Research Foundation of Korea (NRF) grant funded by the Korea Government (MSIT) (Grant 2021R1A2C3006308, 2021R1C1C1013828 and 2021R1A6A1A03039503).

Publisher Copyright:
© 2022 Wiley-VCH GmbH.

All Science Journal Classification (ASJC) codes

Catalysis
Chemistry(all)

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10.1002/anie.202214342

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title = "Synthesis of Subporphyrin Free Bases",

abstract = "BIII subporphyrins are the legitimate ring-contracted porphyrins consisting of three pyrroles and three meso-carbons and their chemistry has been extensively developed since the first synthesis in 2006. However, subporphyrin free bases have never been synthesized, despite tremendous attempts to remove the BIII ion. Here we report that Suzuki–Miyaura coupling between α,α′-diborylated tripyrrane 1 and tetrabromide 5 gave subporphyrin free bases 6, 6 A, and free base dimer 7 in 6 %, 4 %, and 2 % yields as the first examples. Subporphyrin free bases exhibit curved bowl-like structures and distinct 14π-aromaticity. Steady-state and time-resolved spectroscopy revealed that the excited-state behaviors of the subporphyrin free bases are comparable with those of the corresponding BIII subporphyrins. Rotational relaxation processes in the excited states have been revealed, which enhance the electronic interactions with the meso-aryl substituents and between the two subporphyrins.",

author = "Le Liu and Jinseok Kim and Ling Xu and Yutao Rao and Mingbo Zhou and Bangshao Yin and Juwon Oh and Dongho Kim and Atsuhiro Osuka and Jianxin Song",

note = "Funding Information: The work is supported by the National Natural Science Foundation of China (Grant Nos. 22071052, 21772036, 21702057, 21602058), Science and Technology Planning Project of Hunan Province (2018TP1017), Science and Technology Innovation Program of Hunan Province (2021RC4059). The work is also supported by a National Research Foundation of Korea (NRF) grant funded by the Korea Government (MSIT) (Grant 2021R1A2C3006308, 2021R1C1C1013828 and 2021R1A6A1A03039503). Publisher Copyright: {\textcopyright} 2022 Wiley-VCH GmbH.",

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AU - Kim, Jinseok

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AU - Oh, Juwon

AU - Kim, Dongho

AU - Osuka, Atsuhiro

AU - Song, Jianxin

N1 - Funding Information: The work is supported by the National Natural Science Foundation of China (Grant Nos. 22071052, 21772036, 21702057, 21602058), Science and Technology Planning Project of Hunan Province (2018TP1017), Science and Technology Innovation Program of Hunan Province (2021RC4059). The work is also supported by a National Research Foundation of Korea (NRF) grant funded by the Korea Government (MSIT) (Grant 2021R1A2C3006308, 2021R1C1C1013828 and 2021R1A6A1A03039503). Publisher Copyright: © 2022 Wiley-VCH GmbH.

PY - 2022/12/12

Y1 - 2022/12/12

N2 - BIII subporphyrins are the legitimate ring-contracted porphyrins consisting of three pyrroles and three meso-carbons and their chemistry has been extensively developed since the first synthesis in 2006. However, subporphyrin free bases have never been synthesized, despite tremendous attempts to remove the BIII ion. Here we report that Suzuki–Miyaura coupling between α,α′-diborylated tripyrrane 1 and tetrabromide 5 gave subporphyrin free bases 6, 6 A, and free base dimer 7 in 6 %, 4 %, and 2 % yields as the first examples. Subporphyrin free bases exhibit curved bowl-like structures and distinct 14π-aromaticity. Steady-state and time-resolved spectroscopy revealed that the excited-state behaviors of the subporphyrin free bases are comparable with those of the corresponding BIII subporphyrins. Rotational relaxation processes in the excited states have been revealed, which enhance the electronic interactions with the meso-aryl substituents and between the two subporphyrins.

AB - BIII subporphyrins are the legitimate ring-contracted porphyrins consisting of three pyrroles and three meso-carbons and their chemistry has been extensively developed since the first synthesis in 2006. However, subporphyrin free bases have never been synthesized, despite tremendous attempts to remove the BIII ion. Here we report that Suzuki–Miyaura coupling between α,α′-diborylated tripyrrane 1 and tetrabromide 5 gave subporphyrin free bases 6, 6 A, and free base dimer 7 in 6 %, 4 %, and 2 % yields as the first examples. Subporphyrin free bases exhibit curved bowl-like structures and distinct 14π-aromaticity. Steady-state and time-resolved spectroscopy revealed that the excited-state behaviors of the subporphyrin free bases are comparable with those of the corresponding BIII subporphyrins. Rotational relaxation processes in the excited states have been revealed, which enhance the electronic interactions with the meso-aryl substituents and between the two subporphyrins.

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Synthesis of Subporphyrin Free Bases

Abstract

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