1,3-Aza-Brook Rearrangement of Aniline Derivatives: In Situ Generation of 3-Aminoaryne via 1,3-C-(sp2)-to-N Silyl Migration

Young Kyo Jeon; Won Suk Kim

doi:10.1021/acs.orglett.1c02751

1,3-Aza-Brook Rearrangement of Aniline Derivatives: In Situ Generation of 3-Aminoaryne via 1,3-C-(sp²)-to-N Silyl Migration

Young Kyo Jeon, Won Suk Kim

Department of Chemistry & Nanoscience

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

10 Scopus citations

Abstract

The design, synthesis, and validation of 3-aminobenzyne precursors induced by C-(sp2)-to-N 1,3-aza-Brook rearrangement have been achieved, allowing access to diverse aniline derivatives. Through crossover experiments, we demonstrated the intramolecular mechanism of 1,3-C-to-N silyl transfer. To gain insight into the regioselectivity observed in the reactions, we performed density functional theory calculations. Finally, the method was applied to the synthesis of xylanigripones A in five linear steps in an overall yield of 30%.

Original language	English
Pages (from-to)	7545-7549
Number of pages	5
Journal	Organic Letters
Volume	23
Issue number	19
DOIs	https://doi.org/10.1021/acs.orglett.1c02751
State	Published - 1 Oct 2021

Bibliographical note

Funding Information:
This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) (NRF-2019M1A2A2072417, NRF-2021R1H1A2014525, NRF-2021R1A6A1A10039823).

Publisher Copyright:
© 2021 American Chemical Society.

Access to Document

10.1021/acs.orglett.1c02751

Cite this

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title = "1,3-Aza-Brook Rearrangement of Aniline Derivatives: In Situ Generation of 3-Aminoaryne via 1,3-C-(sp2)-to-N Silyl Migration",

abstract = "The design, synthesis, and validation of 3-aminobenzyne precursors induced by C-(sp2)-to-N 1,3-aza-Brook rearrangement have been achieved, allowing access to diverse aniline derivatives. Through crossover experiments, we demonstrated the intramolecular mechanism of 1,3-C-to-N silyl transfer. To gain insight into the regioselectivity observed in the reactions, we performed density functional theory calculations. Finally, the method was applied to the synthesis of xylanigripones A in five linear steps in an overall yield of 30\%. ",

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note = "Funding Information: This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) (NRF-2019M1A2A2072417, NRF-2021R1H1A2014525, NRF-2021R1A6A1A10039823). Publisher Copyright: {\textcopyright} 2021 American Chemical Society.",

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AU - Jeon, Young Kyo

AU - Kim, Won Suk

N1 - Funding Information: This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF) (NRF-2019M1A2A2072417, NRF-2021R1H1A2014525, NRF-2021R1A6A1A10039823). Publisher Copyright: © 2021 American Chemical Society.

PY - 2021/10/1

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N2 - The design, synthesis, and validation of 3-aminobenzyne precursors induced by C-(sp2)-to-N 1,3-aza-Brook rearrangement have been achieved, allowing access to diverse aniline derivatives. Through crossover experiments, we demonstrated the intramolecular mechanism of 1,3-C-to-N silyl transfer. To gain insight into the regioselectivity observed in the reactions, we performed density functional theory calculations. Finally, the method was applied to the synthesis of xylanigripones A in five linear steps in an overall yield of 30%.

AB - The design, synthesis, and validation of 3-aminobenzyne precursors induced by C-(sp2)-to-N 1,3-aza-Brook rearrangement have been achieved, allowing access to diverse aniline derivatives. Through crossover experiments, we demonstrated the intramolecular mechanism of 1,3-C-to-N silyl transfer. To gain insight into the regioselectivity observed in the reactions, we performed density functional theory calculations. Finally, the method was applied to the synthesis of xylanigripones A in five linear steps in an overall yield of 30%.

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