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手性离子对有机催化剂促进烯丙醇的高度对映选择性3-碘环醚化反应。

Chiral ion-pair organocatalyst promotes highly enantioselective 3- iodo-cycloetherification of allyl alcohols.

作者信息

Shen Zhigao, Pan Xixian, Lai Yisheng, Hu Jiadong, Wan Xiaolong, Li Xiaoge, Zhang Hui, Xie Weiqing

机构信息

Shaanxi Key Laboratory of Natural Products & Chemical Biology , College of Science , Northwest A&F University , 22 Xinong Road , Yangling 712100 , China . Email:

State Key Laboratory of Natural Medicines , Jiangsu Key Laboratory of Drug Discovery for Metabolic Diseases , Center of Drug Discovery , China Pharmaceutical University , 24 Tongjiaxiang , Nanjing 210009 , China.

出版信息

Chem Sci. 2015 Dec 1;6(12):6986-6990. doi: 10.1039/c5sc02485d. Epub 2015 Aug 27.

DOI:10.1039/c5sc02485d
PMID:29861937
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC5947518/
Abstract

By designing a novel chiral ion-pair organocatalyst composed of chiral phosphate and DABCO-derived quaternary ammonium, highly enantioselective 3- iodo-cycloetherification of allyl alcohols was achieved using NIS as a halogen source. Based on this reaction, one-pot asymmetric 3- iodo-cycloetherification/Wagner-Meerwein rearrangement of allyl alcohols en route to enantioenriched 2-iodomethyl-2-aryl cycloalkanones was subsequently developed. Due to the participation of adjacent iodine, the Wagner-Meerwein rearrangement of 2-iodomethyl-2-aryl epoxide proceeds with unusual retention of stereoconfiguration.

摘要

通过设计一种由手性磷酸和DABCO衍生的季铵盐组成的新型手性离子对有机催化剂，以NIS作为卤素源实现了烯丙醇的高对映选择性3-碘环醚化反应。基于该反应，随后开发了烯丙醇的一锅法不对称3-碘环醚化/瓦格纳-米尔温重排反应，用于合成对映体富集的2-碘甲基-2-芳基环烷酮。由于相邻碘的参与，2-碘甲基-2-芳基环氧化物的瓦格纳-米尔温重排反应以不寻常的立体构型保持方式进行。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a4e3/5947518/d21b1a00beaf/c5sc02485d-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a4e3/5947518/12c9e3d23f6c/c5sc02485d-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a4e3/5947518/b2cfd674647a/c5sc02485d-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a4e3/5947518/4bf640dcbc87/c5sc02485d-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a4e3/5947518/d21b1a00beaf/c5sc02485d-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a4e3/5947518/12c9e3d23f6c/c5sc02485d-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a4e3/5947518/b2cfd674647a/c5sc02485d-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a4e3/5947518/4bf640dcbc87/c5sc02485d-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/a4e3/5947518/d21b1a00beaf/c5sc02485d-s3.jpg

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本文引用的文献

1
Asymmetric organocatalytic epoxidations: reactions, scope, mechanisms, and applications.不对称有机催化环氧化反应：反应、范围、机理和应用。
Angew Chem Int Ed Engl. 2014 Jul 14;53(29):7406-26. doi: 10.1002/anie.201400241. Epub 2014 Jun 11.
2
Desymmetrization of diolefinic diols by enantioselective amino-thiocarbamate-catalyzed bromoetherification: synthesis of chiral spirocycles.通过对映选择性氨基硫脲催化的溴醚化反应对二烯烃二醇进行去对称化：手性螺环的合成。
Angew Chem Int Ed Engl. 2014 May 12;53(20):5161-4. doi: 10.1002/anie.201310136. Epub 2014 Apr 6.
3
Catalytic asymmetric bromoetherification and desymmetrization of olefinic 1,3-diols with C2-symmetric sulfides.
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添加剂控制的不对称碘环化反应能够实现对 α-和 β-核苷的对映选择性构建。
Nat Commun. 2023 Jan 10;14(1):138. doi: 10.1038/s41467-022-35610-w.
4
Enantioselective Kinetic Resolution/Desymmetrization of -Quinols: A Case Study in Boronic-Acid-Directed Phosphoric Acid Catalysis.α-喹诺醇的对映选择性动力学拆分/去对称化：硼酸导向磷酸催化的案例研究
Adv Synth Catal. 2020 Jan 23;362(2):295-301. doi: 10.1002/adsc.201900816. Epub 2019 Sep 6.
5
Catalytic Dynamic Kinetic Resolutions in Tandem to Construct Two-Axis Terphenyl Atropisomers.串联催化动态动力学拆分构建两轴联苯轴手性异构体。
J Am Chem Soc. 2020 Sep 23;142(38):16461-16470. doi: 10.1021/jacs.0c08057. Epub 2020 Sep 14.
6
Regio- and Enantioselective Bromocyclization of Difluoroalkenes as a Strategy to Access Tetrasubstituted Difluoromethylene-Containing Stereocenters.区域和对映选择性的二氟烯烃溴环化反应作为一种构建四取代二氟亚甲基手性中心的策略。
J Am Chem Soc. 2020 May 13;142(19):8946-8952. doi: 10.1021/jacs.0c02331. Epub 2020 Apr 30.
7
[1,3]/[1,4]-Sulfur atom migration in β-hydroxyalkylphosphine sulfides.β-羟基烷基膦硫化物中[1,3]/[1,4]-硫原子迁移
Beilstein J Org Chem. 2020 Jan 21;16:88-105. doi: 10.3762/bjoc.16.11. eCollection 2020.
8
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手性 C2 对称亚砜催化烯烃 1,3-二醇的不对称溴代醚化和去对称化反应。
J Am Chem Soc. 2014 Apr 16;136(15):5627-30. doi: 10.1021/ja5029155. Epub 2014 Apr 8.
4
Highly asymmetric bromocyclization of tryptophol: unexpected accelerating effect of DABCO-derived bromine complex.色氨酸醇的高度不对称溴环化反应：DABCO 衍生溴络合物的意外加速效应。
Org Lett. 2014 Apr 4;16(7):1908-11. doi: 10.1021/ol5004109. Epub 2014 Mar 25.
5
Asymmetric chlorination/ring expansion for the synthesis of α-quaternary cycloalkanones.不对称氯代/环扩环反应合成α-季碳环烷酮。
Org Lett. 2014 Mar 21;16(6):1810-3. doi: 10.1021/ol5005565. Epub 2014 Mar 11.
6
Chiral β-Iodoamines by Urea-Catalyzed Iodocyclization of Trichloroacetimidates.通过脲催化三氯乙酰亚胺酯的碘环化反应制备手性β-碘代胺
Chem Sci J. 2013 May 1;4(5). doi: 10.1039/C3SC50410G.
7
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Chirality. 2014 Jul;26(7):344-55. doi: 10.1002/chir.22259. Epub 2013 Nov 7.
8
Enantioselective organocatalytic iodination-initiated Wagner-Meerwein rearrangement.对映选择性有机催化碘化引发的 Wagner-Meerwein 重排。
Org Lett. 2013 Nov 15;15(22):5890-3. doi: 10.1021/ol402981z. Epub 2013 Nov 6.
9
Highly enantioselective bromocyclization of tryptamines and its application in the synthesis of (-)-chimonanthine.高对映选择性的色胺溴环化反应及其在（-）-夏佛塔辛合成中的应用。
Angew Chem Int Ed Engl. 2013 Dec 2;52(49):12924-7. doi: 10.1002/anie.201306774. Epub 2013 Oct 10.
10
Recent advances in stereoselective bromofunctionalization of alkenes using N-bromoamide reagents.近年来，使用 N-溴代酰胺试剂对烯烃进行立体选择性溴官能化的研究进展。
Chem Commun (Camb). 2013 Sep 21;49(73):7985-96. doi: 10.1039/c3cc43950j. Epub 2013 Aug 1.