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由降冰片二烯两步合成七环[6.6.0.0²,⁷.0³,⁶.0⁴,¹¹.0⁵,¹⁰]十四烷：笼状组装及合成后功能化的机理

Two-Step Synthesis of Heptacyclo[6.6.0.0 .0 .0 .0 .0 ] tetradecane from Norbornadiene: Mechanism of the Cage Assembly and Post-synthetic Functionalization.

作者信息

Zieliński Adam, Marset Xavier, Golz Christopher, Wolf Lawrence M, Alcarazo Manuel

机构信息

Institut für Organische und Biomolekulare Chemie, Georg August Universität Göttingen, Tammannstr 2, 37077, Göttingen, Germany.

Department of Chemistry, University of Massachusetts Lowell, Lowell, MA, 01854, USA.

出版信息

Angew Chem Int Ed Engl. 2020 Dec 14;59(51):23299-23305. doi: 10.1002/anie.202010766. Epub 2020 Oct 15.

DOI:10.1002/anie.202010766
PMID:32881255
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC7756769/
Abstract

A selective and scalable two-step approach to the dimerization of norbornadiene (NBD) into its thermodynamically most stable dimer, heptacyclo[6.6.0.0 .0 .0 .0 .0 ] tetradecane, (HCTD) is reported. Calculations indicate that the reaction starts with the Rh-catalyzed stepwise homo Diels-Alder cyclisation of NBD into its exo-cis-endo dimer. Treatment of this compound with acid promotes its evolution to HCTD via a [1,2]-sigmatropic rearrangement. The assemblies of 7,12-disubstituted cages from 7-(alkyl/aryl) NBDs, as well as the selective post-synthetic C-H functionalization of the core HCTD scaffold at position C1, or positions C1 and C4 are described.

摘要

报道了一种选择性且可扩展的两步法，用于将降冰片二烯（NBD）二聚化为其热力学上最稳定的二聚体，即七环[6.6.0.0²,⁷.0³,⁶.0⁴,¹¹.0⁵,¹⁰]十四烷（HCTD）。计算表明，该反应始于铑催化的NBD逐步进行同分子狄尔斯-阿尔德环化反应生成其外型-顺式-内型二聚体。用酸处理该化合物可通过[1,2]-σ迁移重排促进其转化为HCTD。描述了由7-(烷基/芳基)NBDs组装7,12-二取代笼状物，以及在核心HCTD支架的C1位或C1和C4位进行选择性合成后C-H官能化的情况。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5d0/7756769/426e125ff0ae/ANIE-59-23299-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5d0/7756769/a672c21d6886/ANIE-59-23299-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5d0/7756769/25efc5d9c69b/ANIE-59-23299-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5d0/7756769/64f195985516/ANIE-59-23299-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5d0/7756769/ced2e8ea577b/ANIE-59-23299-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5d0/7756769/95d14efc3e44/ANIE-59-23299-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5d0/7756769/cd15ed7a19cc/ANIE-59-23299-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5d0/7756769/426e125ff0ae/ANIE-59-23299-g007.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5d0/7756769/a672c21d6886/ANIE-59-23299-g003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5d0/7756769/25efc5d9c69b/ANIE-59-23299-g004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5d0/7756769/64f195985516/ANIE-59-23299-g001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5d0/7756769/ced2e8ea577b/ANIE-59-23299-g005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5d0/7756769/95d14efc3e44/ANIE-59-23299-g002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5d0/7756769/cd15ed7a19cc/ANIE-59-23299-g006.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/f5d0/7756769/426e125ff0ae/ANIE-59-23299-g007.jpg

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2
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J Am Chem Soc. 2017 Apr 5;139(13):4948-4953. doi: 10.1021/jacs.7b01441. Epub 2017 Mar 21.
3
Adamantane in Drug Delivery Systems and Surface Recognition.药物递送系统与表面识别中的金刚烷
Molecules. 2017 Feb 16;22(2):297. doi: 10.3390/molecules22020297.
4
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Acc Chem Res. 2016 Sep 20;49(9):1797-805. doi: 10.1021/acs.accounts.6b00262. Epub 2016 Aug 16.
5
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Org Lett. 2016 Mar 4;18(5):1104-7. doi: 10.1021/acs.orglett.6b00207. Epub 2016 Feb 10.
6
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Chem Rev. 2015 Jul 22;115(14):6719-45. doi: 10.1021/cr500523x. Epub 2015 Jun 23.
7
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