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空间位阻氧杂螺环的立体选择性构建：手性双齿导向基团介导的C(sp)-O键形成

Stereoselective construction of sterically hindered oxaspirocycles chiral bidentate directing group-mediated C(sp)-O bond formation.

作者信息

Kim Yechan, Kim Seoung-Tae, Kang Dahye, Sohn Te-Ik, Jang Eunyoung, Baik Mu-Hyun, Hong Sungwoo

机构信息

Department of Chemistry , Korea Advanced Institute of Science and Technology (KAIST) , Daejeon , 34141 , Korea . Email:

Center for Catalytic Hydrocarbon Functionalizations , Institute for Basic Science (IBS) , Daejeon 34141 , Korea.

出版信息

Chem Sci. 2017 Nov 27;9(6):1473-1480. doi: 10.1039/c7sc04691j. eCollection 2018 Feb 14.

DOI:10.1039/c7sc04691j
PMID:29629170
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5875089/
Abstract

The systematic investigation of chiral bidentate auxiliaries has resulted in the discovery of a chiral 2,2-dimethyl-1-(pyridin-2-yl)propan-1-amine-derived directing group that enables stereoselective palladium(ii)-catalyzed intramolecular C(sp)-O bond formation. This new chiral directing group exhibited high reactivity in the activation of methylene C(sp)-H bonds with excellent levels of stereoselectivity (a diastereomeric ratio of up to 39 : 1), which allowed the construction of a wide range of oxaspirocycles. Mechanistic investigations were also conducted to elucidate the reaction mechanism and understand the origin of the diastereoselectivity. DFT calculations suggest that only modest levels of diastereoselectivity are accomplished at the rate-determining C-H metalation-deprotonation step and the d.r. is further enriched at the reductive elimination step.

摘要

对手性双齿助剂的系统研究导致发现了一种源自手性2,2-二甲基-1-(吡啶-2-基)丙-1-胺的导向基团，该基团能够实现立体选择性钯(II)催化的分子内C(sp)-O键形成。这种新的手性导向基团在亚甲基C(sp)-H键的活化中表现出高反应活性，并具有优异的立体选择性水平（非对映体比例高达39:1），这使得能够构建多种氧杂螺环化合物。还进行了机理研究以阐明反应机理并理解非对映选择性的起源。密度泛函理论计算表明，在速率决定步骤的C-H金属化-去质子化步骤中仅实现了适度水平的非对映选择性，并且在还原消除步骤中非对映体比例进一步富集。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ae99/5875089/8ac456fc8cc2/c7sc04691j-f6.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ae99/5875089/8ac456fc8cc2/c7sc04691j-f6.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ae99/5875089/65a03b3ef5eb/c7sc04691j-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ae99/5875089/262c333f47e0/c7sc04691j-f1.jpg
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https://cdn.ncbi.nlm.nih.gov/pmc/blobs/ae99/5875089/8ac456fc8cc2/c7sc04691j-f6.jpg

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