内炔的串联甲硅烷基甲酰化-巴豆基甲硅烷基化/Tamao氧化反应：一个从简单到复杂的显著例子。
Tandem silylformylation-crotylsilylation/Tamao oxidation of internal alkynes: a remarkable example of generating complexity from simplicity.
作者信息
Spletstoser Jared T, Zacuto Michael J, Leighton James L
机构信息
Department of Chemistry, Columbia University, New York, New York 10027, USA.
出版信息
Org Lett. 2008 Dec 18;10(24):5593-6. doi: 10.1021/ol802489w.
Abstract
The rhodium-catalyzed tandem silylformylation-crotylsilylation reaction has been extended to include internal alkynes. Tamao oxidation of the initial product leads to the production of a substituted enol, which undergoes highly diastereoselective tautomerization. The resulting one-pot procedure fashions three new stereocenters, a ketone, and a terminal alkene from a butenyl group, a propynyl group, a silyl hydride, H2O2, and CO.
摘要
铑催化的串联甲硅烷基甲酰化-巴豆基硅烷化反应已扩展到包括内炔烃。初始产物的玉尾氧化导致生成取代烯醇，该烯醇发生高度非对映选择性互变异构。由此产生的一锅法从一个丁烯基、一个丙炔基、一个硅烷氢化物、过氧化氢和一氧化碳形成三个新的立体中心、一个酮和一个末端烯烃。
相似文献
1
Tandem silylformylation-crotylsilylation/Tamao oxidation of internal alkynes: a remarkable example of generating complexity from simplicity.内炔的串联甲硅烷基甲酰化-巴豆基甲硅烷基化/Tamao氧化反应：一个从简单到复杂的显著例子。
Org Lett. 2008 Dec 18;10(24):5593-6. doi: 10.1021/ol802489w.
2
An "aprotic" Tamao oxidation/syn-selective tautomerization reaction for the efficient synthesis of the C1-C9 fragment of fludelone.一种“非质子”的 Tamao 氧化/顺反选择性互变异构反应，用于高效合成 fludelone 的 C1-C9 片段。
Org Lett. 2012 Sep 21;14(18):4890-3. doi: 10.1021/ol302221s. Epub 2012 Sep 5.
3
Desymmetrization of 4-dimethylsiloxy-1,6-heptadiynes through sequential double silylformylation.通过连续双甲硅烷基甲酰化实现4-二甲基硅氧基-1,6-庚二炔的去对称化
Org Lett. 2001 May 3;3(9):1303-5. doi: 10.1021/ol0156594.
4
Tandem intramolecular silylformylation-crotylsilylation: highly efficient synthesis of polyketide fragments.串联分子内甲硅烷基甲酰化-巴豆基甲硅烷基化反应：聚酮片段的高效合成
J Am Chem Soc. 2002 Jul 10;124(27):7890-1. doi: 10.1021/ja026511y.
5
Beyond the Roche ester: a new approach to polypropionate stereotriad synthesis.超越罗氏酯：一种新的聚合丙酸立体三联合成方法。
Org Lett. 2014 Feb 21;16(4):1180-3. doi: 10.1021/ol500051e. Epub 2014 Feb 6.
6
Rhodium-catalysed synthesis of multi-substituted silylindenes from aryl alkynes and hydrosilanes via C-H bond activation.铑催化通过碳氢键活化由芳基炔烃和硅烷合成多取代硅基茚。
Chem Commun (Camb). 2015 May 4;51(36):7685-8. doi: 10.1039/c5cc01569c.
7
One-pot synthesis of highly substituted 4-acetonylindoles via sequential dearomatization and silver-catalyzed domino reaction.通过连续去芳构化和银催化多米诺反应一锅法合成高度取代的4-乙酰基吲哚。
Org Lett. 2014 Jul 3;16(13):3600-3. doi: 10.1021/ol501678v. Epub 2014 Jun 25.
8
Rhodium-catalyzed redox-neutral coupling of phenidones with alkynes.铑催化的非那吡啶酮与炔烃的氧化还原中性偶联反应。
Org Biomol Chem. 2017 Jul 21;15(27):5701-5708. doi: 10.1039/c7ob01271c. Epub 2017 Jun 26.
9
Sterically directed iridium-catalyzed hydrosilylation of alkenes in the presence of alkynes.在炔烃存在下，空间定向的铱催化烯烃的硅氢化反应。
Org Lett. 2014 Mar 7;16(5):1330-3. doi: 10.1021/ol5000549. Epub 2014 Feb 19.
10
Tandem cyclization of alkynes via rhodium alkynyl and alkenylidene catalysis.通过铑炔基和亚乙烯基催化实现炔烃的串联环化反应。
J Am Chem Soc. 2006 Nov 22;128(46):14818-9. doi: 10.1021/ja066374v.
引用本文的文献
1
Silylation reactions on nanoporous gold homolytic Si-H activation of silanes.纳米多孔金上的硅烷化反应——硅烷的均裂Si-H活化
Chem Sci. 2018 Apr 30;9(21):4808-4813. doi: 10.1039/c8sc01427b. eCollection 2018 Jun 7.
2
Synthesis and Evaluation of a Linkable Functional Group-Equipped Analogue of the Epothilones.埃坡霉素的一种带有可连接官能团类似物的合成与评价
ACS Med Chem Lett. 2017 May 1;8(7):701-704. doi: 10.1021/acsmedchemlett.7b00131. eCollection 2017 Jul 13.
3
Local Desymmetrization through Diastereotopic Group Selection: An Enabling Strategy for Natural Product Synthesis.通过非对映异位基团选择实现局部去对称化：天然产物合成的一种赋能策略。
European J Org Chem. 2017 Mar 17;2017(11):1381-1390. doi: 10.1002/ejoc.201601481. Epub 2017 Feb 7.
4
Chemoselective Alteration of Fluorophore Scaffolds as a Strategy for the Development of Ratiometric Chemodosimeters.作为比率型化学计量型化学传感器开发策略的荧光团支架的化学选择性修饰。
Angew Chem Int Ed Engl. 2017 Apr 3;56(15):4197-4200. doi: 10.1002/anie.201612628. Epub 2017 Mar 20.
5
A Highly Stereoselective, Efficient, and Scalable Synthesis of the C(1)-C(9) Fragment of the Epothilones.埃坡霉素C(1)-C(9)片段的高度立体选择性、高效且可扩展的合成
Org Lett. 2015 Dec 4;17(23):5858-61. doi: 10.1021/acs.orglett.5b03034. Epub 2015 Nov 12.
6
Toward a more step-economical and scalable synthesis of spongistatin 1 to facilitate cancer drug development efforts.朝着更具步骤经济性和可扩展性的海绵他汀1合成方向发展，以促进癌症药物开发工作。
Chem Sci. 2013 Apr 1;4(4):1497-1501. doi: 10.1039/C3SC22186E.
7
Complex fragment coupling by crotylation: A powerful tool for polyketide natural product synthesis.通过巴豆酰化进行复杂片段偶联：聚酮天然产物合成的有力工具。
Chem Sci. 2012 Nov 1;3(11):3326-3330. doi: 10.1039/C2SC21325G.
8
Beyond the Roche ester: a new approach to polypropionate stereotriad synthesis.超越罗氏酯：一种新的聚合丙酸立体三联合成方法。
Org Lett. 2014 Feb 21;16(4):1180-3. doi: 10.1021/ol500051e. Epub 2014 Feb 6.
9
A highly step-economical synthesis of dictyostatin.一种高度步骤经济性的软海绵素合成方法。
Angew Chem Int Ed Engl. 2013 Jun 24;52(26):6757-61. doi: 10.1002/anie.201302565. Epub 2013 May 10.
10
An "aprotic" Tamao oxidation/syn-selective tautomerization reaction for the efficient synthesis of the C1-C9 fragment of fludelone.一种“非质子”的 Tamao 氧化/顺反选择性互变异构反应，用于高效合成 fludelone 的 C1-C9 片段。
Org Lett. 2012 Sep 21;14(18):4890-3. doi: 10.1021/ol302221s. Epub 2012 Sep 5.
本文引用的文献
1
Studies on a urea-directed Stork-Crabtree hydrogenation. Synthesis of the C1-C9 subunit of (+)-zincophorin.关于尿素导向的斯托克-克拉布特里氢化反应的研究。（+）-锌卟啉C1-C9亚基的合成。
J Org Chem. 2007 Dec 7;72(25):9722-31. doi: 10.1021/jo7017922. Epub 2007 Nov 3.
2
Total synthesis of dolabelide D.多拉贝利德D的全合成。
J Am Chem Soc. 2006 Mar 8;128(9):2796-7. doi: 10.1021/ja058692k.
3
Advances in the total synthesis of biologically important marine macrolides.具有生物学重要性的海洋大环内酯类化合物全合成研究进展
Chem Rev. 2005 Dec;105(12):4237-313. doi: 10.1021/cr040614c.
4
Efficient asymmetric synthesis of (+)-SCH 351448.(+)-SCH 351448的高效不对称合成。
Org Lett. 2005 Aug 18;7(17):3809-12. doi: 10.1021/ol0515006.
5
Stereoselective total synthesis of the ionophore antibiotic zincophorin.离子载体抗生素锌霉素的立体选择性全合成。
Angew Chem Int Ed Engl. 2004 Aug 20;43(33):4341-5. doi: 10.1002/anie.200460434.
6
Total synthesis of zincophorin and its methyl ester.锌光菌素及其甲酯的全合成。
J Org Chem. 2004 Jul 9;69(14):4626-47. doi: 10.1021/jo0496042.
7
Approach to the synthesis of dolabelides A and B: fragment synthesis by tandem silylformylation-crotylsilylation.多拉贝利德A和B的合成方法：通过串联甲硅烷基甲酰化-巴豆基甲硅烷基化进行片段合成。
Org Lett. 2003 Sep 18;5(19):3535-7. doi: 10.1021/ol035431b.
8
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.α-甲基-β-羟基醛与烯丙基三氟硅烷和巴豆基三氟硅烷的烯丙基化和巴豆基化反应的立体化学。反式、反式-二丙酸酯立体三联体的合成以及与2,3-反式和2,3-顺式-α-甲基-β-羟基醛反应的立体发散途径。
J Org Chem. 2003 Feb 21;68(4):1319-33. doi: 10.1021/jo0267908.
9
Catalytic asymmetric silane alcoholysis: practical access to chiral silanes.催化不对称硅烷醇解：手性硅烷的实用合成方法
J Am Chem Soc. 2003 Feb 5;125(5):1190-1. doi: 10.1021/ja0283201.
10
Tandem intramolecular silylformylation-crotylsilylation: highly efficient synthesis of polyketide fragments.串联分子内甲硅烷基甲酰化-巴豆基甲硅烷基化反应：聚酮片段的高效合成
J Am Chem Soc. 2002 Jul 10;124(27):7890-1. doi: 10.1021/ja026511y.
Zotero 插件