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α-氟代酮的构象偏好可能会影响它们的反应活性。

Conformational preferences of α-fluoroketones may influence their reactivity.

作者信息

Pattison Graham

机构信息

Department of Chemistry, University of Warwick, Gibbet Hill Road, Coventry CV4 7AL, UK.

出版信息

Beilstein J Org Chem. 2017 Dec 29;13:2915-2921. doi: 10.3762/bjoc.13.284. eCollection 2017.

DOI:10.3762/bjoc.13.284
PMID:29564019
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5753061/
Abstract

Fluorine has been shown in many cases to impart specific and predictable effects on molecular conformation. Here it is shown that these conformational effects may have an influence on reactivity through studying the relative reactivity of various α-halogenated ketones towards borohydride reduction. These results demonstrate that the α-fluoro ketones are in fact a little less reactive than the corresponding α-chloro and α-bromo derivatives. It is suggested, supported by computation, that this effect is due to reactive conformations in which the C-X bond is orthogonal to the carbonyl group for good orbital overlap being disfavoured in the case of fluoro ketones.

摘要

在许多情况下，氟已被证明会对分子构象产生特定且可预测的影响。本文通过研究各种α-卤代酮对硼氢化还原反应的相对反应活性，表明这些构象效应可能会对反应活性产生影响。这些结果表明，α-氟代酮的反应活性实际上比相应的α-氯代和α-溴代衍生物略低。计算结果支持了这一观点，即这种效应是由于在氟代酮中，不利于C-X键与羰基呈正交以实现良好轨道重叠的反应性构象。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f856/5753061/694313f296f0/Beilstein_J_Org_Chem-13-2915-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f856/5753061/630524376076/Beilstein_J_Org_Chem-13-2915-g011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f856/5753061/536deb480822/Beilstein_J_Org_Chem-13-2915-g012.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f856/5753061/742b819f0859/Beilstein_J_Org_Chem-13-2915-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f856/5753061/6f47bd08d7e6/Beilstein_J_Org_Chem-13-2915-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f856/5753061/7a7137c54f02/Beilstein_J_Org_Chem-13-2915-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f856/5753061/217c57cf447a/Beilstein_J_Org_Chem-13-2915-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f856/5753061/5cbeecc4dcd8/Beilstein_J_Org_Chem-13-2915-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f856/5753061/45ab5bccb93a/Beilstein_J_Org_Chem-13-2915-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f856/5753061/b21c8af4a31c/Beilstein_J_Org_Chem-13-2915-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f856/5753061/6d25ffcd428d/Beilstein_J_Org_Chem-13-2915-g013.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f856/5753061/e65ec6e31f8e/Beilstein_J_Org_Chem-13-2915-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f856/5753061/694313f296f0/Beilstein_J_Org_Chem-13-2915-g010.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f856/5753061/630524376076/Beilstein_J_Org_Chem-13-2915-g011.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f856/5753061/536deb480822/Beilstein_J_Org_Chem-13-2915-g012.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f856/5753061/742b819f0859/Beilstein_J_Org_Chem-13-2915-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f856/5753061/6f47bd08d7e6/Beilstein_J_Org_Chem-13-2915-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f856/5753061/7a7137c54f02/Beilstein_J_Org_Chem-13-2915-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f856/5753061/217c57cf447a/Beilstein_J_Org_Chem-13-2915-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f856/5753061/5cbeecc4dcd8/Beilstein_J_Org_Chem-13-2915-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f856/5753061/45ab5bccb93a/Beilstein_J_Org_Chem-13-2915-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f856/5753061/b21c8af4a31c/Beilstein_J_Org_Chem-13-2915-g008.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f856/5753061/6d25ffcd428d/Beilstein_J_Org_Chem-13-2915-g013.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f856/5753061/e65ec6e31f8e/Beilstein_J_Org_Chem-13-2915-g009.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f856/5753061/694313f296f0/Beilstein_J_Org_Chem-13-2915-g010.jpg

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