Nickel-Catalyzed Formal [3+2+2] Cycloadditions of Bis(trimethylsilyl)cyclopropanone withDiynes: A Concise Approach to Functionalized Azulene Derivatives
- 1Meiji Pharmaceutical University, 2 -522-1, Kiyose, Noshio, Tokyo, Japan, 204-8588
- 2SPERA PHARMA, Inc. Osaka R&D Center, Chemical R&D Laboratory, 17-85, Jusohonmachi 2-chome, Yodogawa-ku, Osaka, Japan, 532-0024
Abstract
consequently, developing efficient methods for their preparation is important. Herein, we report the development of formal [3+2+2] cycloaddition chemistry involving 1,6-diynes and cis-2,3-bis(trimethylsilyl)cyclopropanone as a new synthetic approach to functionalized azulene derivatives. The azulene framework is efficiently constructed using the developed reaction, with synthetically versatile functional groups introduced in a single operation. An unusual rearrangement process consistent with a formal [1,7]-silyl migration from the C7 to C6 position of the azulene framework was observed during the course of the transformation. The synthetic utility of the method was demonstrated by further transforming the resulting silylated azulene derivatives into a variety of 1functionalized azulenes. This study provides a new strategy for constructing and functionalizing azulene skeletons as well as new insight into the reactivities of cyclopropanone-derived intermediates.
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BibTeX
@misc{sato2026nickelcatalyzed,
title = {{Nickel-Catalyzed Formal [3+2+2] Cycloadditions of Bis(trimethylsilyl)cyclopropanone withDiynes: A Concise Approach to Functionalized Azulene Derivatives}},
author = {Yuki Sato and Sayaka Ohrui and Masanori Tayu and Satoshi Yagi and Mutsuki Kato and Kuniyoshi Miki and Keiyo Nakai and Mitsuhisa Yamano and Nozomi Saito},
howpublished = {ChemRxiv},
year = {2026},
month = sep,
doi = {10.26434/chemrxiv.15000398/v3},
url = {https://chemrxiv.org/doi/full/10.26434/chemrxiv.15000398/v3},
note = {CC BY},
}
RIS
TY - UNPB
TI - Nickel-Catalyzed Formal [3+2+2] Cycloadditions of Bis(trimethylsilyl)cyclopropanone withDiynes: A Concise Approach to Functionalized Azulene Derivatives
AU - Yuki Sato
AU - Sayaka Ohrui
AU - Masanori Tayu
AU - Satoshi Yagi
AU - Mutsuki Kato
AU - Kuniyoshi Miki
AU - Keiyo Nakai
AU - Mitsuhisa Yamano
AU - Nozomi Saito
PY - 2026
DA - 2026/09/20
PB - ChemRxiv
DO - 10.26434/chemrxiv.15000398/v3
UR - https://chemrxiv.org/doi/full/10.26434/chemrxiv.15000398/v3
AB - consequently, developing efficient methods for their preparation is important. Herein, we report the development of formal [3+2+2] cycloaddition chemistry involving 1,6-diynes and cis-2,3-bis(trimethylsilyl)cyclopropanone as a new synthetic approach to functionalized azulene derivatives. The azulene framework is efficiently constructed using the developed reaction, with synthetically versatile functional groups introduced in a single operation. An unusual rearrangement process consistent with a formal [1,7]-silyl migration from the C7 to C6 position of the azulene framework was observed during the course of the transformation. The synthetic utility of the method was demonstrated by further transforming the resulting silylated azulene derivatives into a variety of 1functionalized azulenes. This study provides a new strategy for constructing and functionalizing azulene skeletons as well as new insight into the reactivities of cyclopropanone-derived intermediates.
ER -