硅氧杂环戊烯作为分子内狄尔斯-阿尔德反应中亲双烯体连接的导向基团。
Siloxacyclopentenes as dienophile-linked directing groups in intramolecular Diels-Alder reactions.
作者信息
Halvorsen Geoff T, Roush William R
机构信息
Department of Chemistry, Scripps-Florida, Jupiter, Florida 33458, USA.
出版信息
Org Lett. 2008 Nov 20;10(22):5313-6. doi: 10.1021/ol802266s. Epub 2008 Oct 28.
Abstract
The synthesis and intramolecular Diels-Alder reactions of trienes 5 and 6 with a siloxacyclopentene-constrained dienophile are described. These reactions provide the primary cycloadducts 7 and 8 with high diastereoselectivity. These cycloadducts possess trans-relationships between the ring fusion proton and the adjacent C(1) alkoxy group and can be further elaborated to alcohols 9 and 11 (via protiodesilylation) or to 10 and 12 (via Fleming-Tamao oxidation) depending on the substitutent R.
摘要
描述了三烯5和6与硅氧杂环戊烯受限亲双烯体的合成及分子内狄尔斯-阿尔德反应。这些反应以高非对映选择性提供了主要的环加成产物7和8。这些环加成产物在环融合质子与相邻的C(1)烷氧基之间具有反式关系，并且根据取代基R的不同，可以进一步转化为醇9和11（通过脱硅反应）或10和12（通过弗莱明-玉尾氧化反应）。
相似文献
1
Siloxacyclopentenes as dienophile-linked directing groups in intramolecular Diels-Alder reactions.
Org Lett. 2008 Nov 20;10(22):5313-6. doi: 10.1021/ol802266s. Epub 2008 Oct 28.
2
Intramolecular Diels-Alder reactions of siloxacyclopentene constrained trienes.
Org Lett. 2007 May 24;9(11):2243-6. doi: 10.1021/ol070858u. Epub 2007 May 5.
3
Intramolecular Diels-Alder reactions of cyclopropenone ketals.
Org Lett. 2010 Aug 6;12(15):3540-3. doi: 10.1021/ol101375a.
4
Torquoselective ring closures of chiral amido trienes derived from allenamides. A tandem allene isomerization-pericyclic ring-closure-intramolecular Diels-Alder cycloaddition.
Org Lett. 2010 Mar 19;12(6):1152-5. doi: 10.1021/ol902821w.
5
Intramolecular Diels-Alder reactions using alpha-methylene lactones as dienophile.
J Org Chem. 2002 Apr 19;67(8):2474-80. doi: 10.1021/jo016116a.
6
Boron and Silicon-Substituted 1,3-Dienes and Dienophiles and Their Use in Diels-Alder Reactions.
Molecules. 2020 Aug 16;25(16):3740. doi: 10.3390/molecules25163740.
7
Formal [2 + 2 + 2] cycloaddition strategy based on an intramolecular propargylic ene reaction/Diels-Alder cycloaddition cascade.
J Am Chem Soc. 2010 Aug 18;132(32):11039-41. doi: 10.1021/ja1053829.
8
Origins of the Endo and Exo Selectivities in Cyclopropenone, Iminocyclopropene, and Triafulvene Diels-Alder Cycloadditions.
J Org Chem. 2018 Mar 16;83(6):3164-3170. doi: 10.1021/acs.joc.8b00025. Epub 2018 Mar 7.
9
Intramolecular Diels-Alder reactions of ester linked 1,3,9-decatrienes: cis/trans selectivity in thermal and Lewis acid promoted reactions of ethylene-tethered and benzo-tethered systems.
J Org Chem. 2006 Aug 4;71(16):6099-109. doi: 10.1021/jo0607818.
10
Nucleophilic addition to silyl-protected five-membered ring oxocarbenium ions governed by stereoelectronic effects.
J Org Chem. 2013 Jul 5;78(13):6609-21. doi: 10.1021/jo400945j. Epub 2013 Jun 24.
引用本文的文献
1
Anion relay chemistry: access to the type II ARC reaction manifold through a fundamentally different reaction pathway exploiting 1-oxa-2-silacyclopentanes and related congeners.
Angew Chem Int Ed Engl. 2011 Sep 12;50(38):8904-7. doi: 10.1002/anie.201103886. Epub 2011 Aug 10.
2
Stereoselective Synthesis of the Decahydrofluorene Core of the Hirsutellones.
Tetrahedron Lett. 2011 Apr 27;52(17):2072-2075. doi: 10.1016/j.tetlet.2010.10.111.
本文引用的文献
1
Total synthesis of (-)-spinosyn A: examination of structural features that govern the stereoselectivity of the key transannular Diels-Alder reaction.
J Org Chem. 2008 Mar 7;73(5):1818-29. doi: 10.1021/jo7024515. Epub 2008 Jan 24.
2
Intramolecular Diels-Alder reactions of siloxacyclopentene constrained trienes.
Org Lett. 2007 May 24;9(11):2243-6. doi: 10.1021/ol070858u. Epub 2007 May 5.
3
Recent advances in natural product synthesis by using intramolecular Diels-Alder reactions.
Chem Rev. 2005 Dec;105(12):4779-807. doi: 10.1021/cr040632u.
4
Unusual Tandem alkynylation and trans-hydrosilylation to form oxasilacyclopentenes.
Org Lett. 2005 Oct 27;7(22):4995-8. doi: 10.1021/ol051996r.
5
Efficient protiodesilylation of unactivated C(sp3)-SiMe2Ph bonds using tetrabutylammonium fluoride.
Org Lett. 2005 Jun 9;7(12):2405-8. doi: 10.1021/ol0506821.
6
Stereochemistry of the allylation and crotylation reactions of alpha-methyl-beta-hydroxy aldehydes with allyl- and crotyltrifluorosilanes. Synthesis of anti,anti-dipropionate stereotriads and stereodivergent pathways for the reactions with 2,3-anti- and 2,3-syn-alpha-methyl-beta-hydroxy aldehydes.
J Org Chem. 2003 Feb 21;68(4):1319-33. doi: 10.1021/jo0267908.
7
Application of the intramolecular vinylogous Morita-Baylis-Hillman reaction toward the synthesis of the spinosyn A tricyclic nucleus.
Org Lett. 2002 Sep 5;4(18):3157-60. doi: 10.1021/ol026540d.
8
Studies on the synthesis of (-)-spinosyn a: application of the steric directing group strategy to transannular Diels-Alder reactions.
J Org Chem. 2002 Jun 14;67(12):4316-24. doi: 10.1021/jo025580s.
Zotero 插件