General Synthesis of Cyclopropanols via Organometallic Addition to 1-Sulfonylcyclopropanols as Cyclopropanone Precursors
Roger Machín Rivera, Yujin Jang, Christopher M. Poteat and Vincent N. G. Lindsay*
*Department of Chemistry, North Carolina State University, 2620 Yarbrough Drive, Raleigh, North Carolina 27695, United States,
Email: vlindsa
ncsu.edu
R. M. Rivera, Y. Jang, C. M. Poteat, V. N. G. Lindsay, Org. Lett., 2020, 22, 6510-6515.
DOI: 10.1021/acs.orglett.0c02303
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Abstract
The addition of diverse organometallic reagents to 1-phenylsulfonylcyclopropanols enables a simple and high-yielding synthesis of 1-substituted cyclopropanols. The transformation is amenable to sp-, sp2-, or sp3-hybridized organometallic C-nucleophiles under mild conditions, and the use of enantioenriched substrates led to highly diastereoselective additions.
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Details
The document discusses a novel method for synthesizing 1-substituted cyclopropanols through the addition of organometallic reagents to 1-phenylsulfonylcyclopropanols, which act as in situ precursors to cyclopropanones. This approach addresses the challenge of creating enantioenriched tertiary cyclopropanols, which are valuable in the synthesis of complex natural products and pharmaceuticals. The method is versatile, accommodating sp-, sp2-, and sp3-hybridized organometallic C-nucleophiles under mild conditions, and achieves high yields and diastereoselectivity. The study also explores the use of MeMgBr as an external base to trigger the initial equilibration to cyclopropanone, enhancing the reaction's efficiency and yield. Additionally, the research demonstrates the synthesis of optically active cyclopropanols using enantioenriched substrates. The document highlights the potential of these cyclopropanols for further functionalization through homoenolate chemistry, enabling the creation of β-functionalized ketones in a one-pot, sequential fashion. This work represents a significant advancement in the field of organic synthesis, providing a general and high-yielding method for producing tertiary cyclopropanols, which were previously difficult to obtain in enantioenriched forms.
Key Words
ID: J54-Y2020
