その他令和8年6月16日
政府調達に関する概要とデータ処理・モデル訓練の詳細
出典：官報発行サイトの掲載情報をもとに整理しています。重要な確認は公式原文を基準にしてください。
出典・注意
官報発行サイトの掲載情報をもとに整理しています。重要な確認は公式原文を基準にしてください。
本文と原文の対照
まず左側の本文を読み、必要な箇所だけ原文ページで確認できる構成です。
← 同日の官報に戻る
原文対照の表示オプション
A General Strategy for the Synthesis of Functionalized
Cyclopropanes via a Copper-Catalyzed Three-Component
Reaction of Alkynes, Diazo Compounds, and Allylic Halides
Yongming Deng,† Qianqian Qiu,† Hongwei Qian,*‡ K. C. M. Kwok,§ and Shifa Zhu*,†
†Department of Chemistry, University of South Florida, Tampa, Florida 33620, United States
‡College of Pharmacy, Nanjing Tech University, Nanjing 211816, China
§Department of Chemistry, The Hong Kong University of Science and Technology, Clear Water Bay, Kowloon, Hong Kong SAR, China
Supporting Information
ABSTRACT: A general strategy for the synthesis of functionalized cyclopropanes has been developed through a copper-catalyzed three-component reaction of alkynes, diazo compounds, and allylic halides. This method provides a straightforward approach to access various substituted cyclopropanes with high efficiency and selectivity.
The development of efficient methods for the construction of cyclopropane rings is of great importance in organic synthesis due to their widespread presence in natural products and pharmaceuticals. Traditional approaches often suffer from limited substrate scope or harsh reaction conditions. Herein, we report a novel copper-catalyzed protocol that overcomes these limitations.
In this study, we explored the reactivity of terminal alkynes with ethyl diazoacetate (EDA) and allylic bromides under mild conditions. The use of CuI as the catalyst and Cs2CO3 as the base proved to be optimal, affording the desired cyclopropane derivatives in good yields.
| Entry | R1 | R2 | Yield (%) |
| 1 | Ph | H | 85 |
| 2 | p-MeC6H4 | H | 82 |
| 3 | p-ClC6H4 | H | 78 |
| 4 | n-Bu | H | 75 |
| 5 | Ph | Me | 80 |
Mechanistic studies suggest that the reaction proceeds via a copper-carbene intermediate generated from the decomposition of the diazo compound. Subsequent insertion into the alkyne followed by nucleophilic attack by the allylic halide leads to the formation of the cyclopropane ring.
Furthermore, the scope of this transformation was extended to include internal alkynes and different types of allylic halides. Notably, the reaction tolerates a wide range of functional groups, including esters, ethers, and halogens, making it a versatile tool for synthetic chemists.
In conclusion, we have developed a robust and efficient method for the synthesis of functionalized cyclopropanes. This work not only expands the toolbox for cyclopropane synthesis but also opens new avenues for the exploration of copper-catalyzed multicomponent reactions.
Experimental procedures, characterization data, and copies of NMR spectra for all new compounds are provided in the Supporting Information. Crystallographic data for compound 3a have been deposited with the Cambridge Crystallographic Data Centre (CCDC 123456).
Acknowledgment: We thank the National Science Foundation (Grant No. CHE-1234567) for financial support. We also acknowledge the assistance of Dr. John Doe in obtaining the X-ray crystal structure.
References:
(1) Smith, A. B.; Jones, C. D. J. Org. Chem. 2020, 85, 1234.
(2) Brown, E. F.; Green, G. H. Angew. Chem. Int. Ed. 2019, 58, 5678.
(3) White, I. J.; Black, K. L. Chem. Rev. 2018, 118, 9012.
読み込み中...
テキスト領域
選択中
非公開 (PII)
関連するその他
関連する新着公告を見逃さないために
Pro プランでは会社名・機関名・キーワードを監視条件として保存し、新着掲載を継続確認できます。14日間無料で試せます。
監視機能の詳細を見る →