乙酰氧基 Meldrum's 酸：在钯催化的不对称烯丙基烷基化反应中一种多功能的酰基阴离子等价物。
Acetoxy Meldrum's acid: a versatile acyl anion equivalent in the Pd-catalyzed asymmetric allylic alkylation.
机构信息
Department of Chemistry, Stanford University, Stanford, California 94305-5080, USA.
出版信息
Org Lett. 2011 Jun 17;13(12):3222-5. doi: 10.1021/ol2011242. Epub 2011 May 26.
Abstract
Acetoxy Meldrum's acid can serve as a versatile acyl anion equivalent in the Pd-catalyzed asymmetric allylic alkylation. The reaction of this nucleophile with various meso and racemic electrophiles afforded alkylated products in high yields and enantiopurities. These enantioenriched products are versatile intermediates that can be further functionalized using nitrogen- and oxygen-centered nucleophiles, affording versatile scaffolds for the synthesis of nucleoside analogues. These scaffolds were used to complete formal syntheses of the anti-HIV drugs carbovir, abacavir, and the antibiotic aristeromycin.
摘要
醋乙氧甲泼尼龙酸可以作为钯催化不对称烯丙基烷基化反应中的多功能酰基阴离子等价物。该亲核试剂与各种内消旋和外消旋亲电试剂反应，以高产率和对映选择性得到烷基化产物。这些对映体富集的产物是多功能的中间体，可以进一步用氮和氧中心亲核试剂进行官能化，为核苷类似物的合成提供了多功能的支架。这些支架被用于完成抗 HIV 药物卡罗维、阿巴卡韦和抗生素阿里斯特霉素的正式合成。
相似文献
1
Acetoxy Meldrum's acid: a versatile acyl anion equivalent in the Pd-catalyzed asymmetric allylic alkylation.乙酰氧基 Meldrum's 酸：在钯催化的不对称烯丙基烷基化反应中一种多功能的酰基阴离子等价物。
Org Lett. 2011 Jun 17;13(12):3222-5. doi: 10.1021/ol2011242. Epub 2011 May 26.
2
Palladium-catalyzed asymmetric allylic alkylation of electron-deficient pyrroles with meso electrophiles.钯催化的缺电子吡咯与内消旋亲电试剂的不对称烯丙基烷基化反应。
Org Lett. 2012 May 4;14(9):2254-7. doi: 10.1021/ol3006584. Epub 2012 Apr 16.
3
Hydrogen-bond-activated palladium-catalyzed allylic alkylation via allylic alkyl ethers: challenging leaving groups.氢键活化钯催化的烯丙基烷基化反应通过烯丙基烷基醚：具有挑战性的离去基团。
Org Lett. 2014 Mar 21;16(6):1570-3. doi: 10.1021/ol5000988. Epub 2014 Mar 12.
4
Pd-catalyzed asymmetric allylic alkylation of pyrazol-5-ones with allylic alcohols: the role of the chiral phosphoric acid in C-O bond cleavage and stereocontrol.钯催化吡唑-5-酮与烯丙醇的不对称烯丙基烷基化反应：手性磷酸在 C-O 键断裂和立体控制中的作用。
J Am Chem Soc. 2013 Jun 26;135(25):9255-8. doi: 10.1021/ja402740q. Epub 2013 Jun 14.
5
A convergent Pd-catalyzed asymmetric allylic alkylation of dl- and meso-divinylethylene carbonate: enantioselective synthesis of (+)-australine hydrochloride and formal synthesis of isoaltholactone.钯催化的dl-和内消旋二乙烯基碳酸酯的收敛不对称烯丙基烷基化反应：（+）-澳洲茄胺盐酸盐的对映选择性合成及异去甲半边莲内酯的形式合成
Chemistry. 2007;13(34):9547-60. doi: 10.1002/chem.200700832.
6
Enantioselective Pd-Catalyzed Allylic Alkylation Reactions of Dihydropyrido[1,2-a]indolone Substrates: Efficient Syntheses of (-)-Goniomitine, (+)-Aspidospermidine, and (-)-Quebrachamine.手性钯催化二氢吡啶并[1,2-a]吲哚酮底物的烯丙基烷基化反应：(-)-戈米辛、(+)-阿朴西多滨和(-)-奎那克林的高效合成。
Angew Chem Int Ed Engl. 2016 Oct 17;55(43):13529-13532. doi: 10.1002/anie.201608138. Epub 2016 Sep 26.
7
Cyclobutenes: At a Crossroad between Diastereoselective Syntheses of Dienes and Unique Palladium-Catalyzed Asymmetric Allylic Substitutions.环丁烯：二烯的非对映选择性合成与独特的钯催化不对称烯丙基取代之间的十字路口。
Acc Chem Res. 2016 Nov 15;49(11):2444-2458. doi: 10.1021/acs.accounts.6b00375. Epub 2016 Oct 31.
8
Asymmetric synthesis of 4'-ethoxy-2',3'-didehydro-2',3'-dideoxynucleosides by palladium-catalyzed kinetic discrimination between the corresponding diastereoisomeric lactol acetates.通过钯催化相应非对映异构乳糖醇乙酸酯之间的动力学区分实现4'-乙氧基-2',3'-二脱氢-2',3'-二脱氧核苷的不对称合成。
J Org Chem. 2002 Jun 14;67(12):4076-80. doi: 10.1021/jo011074b.
9
Pd asymmetric allylic alkylation (AAA). A powerful synthetic tool.钯催化不对称烯丙基烷基化反应（AAA）：一种强大的合成工具。
Chem Pharm Bull (Tokyo). 2002 Jan;50(1):1-14. doi: 10.1248/cpb.50.1.
10
Highly versatile Pd-thioether-phosphite catalytic systems for asymmetric allylic alkylation, amination, and etherification reactions.高度多功能的 Pd-硫醚-亚磷酸酯催化体系，用于不对称烯丙基烷基化、氨基化和醚化反应。
Org Lett. 2014 Apr 4;16(7):1892-5. doi: 10.1021/ol500758y. Epub 2014 Mar 24.
引用本文的文献
1
Supported Ionic Liquid Phase (SILP) Allylic Alkylation of Amines in Continuous Flow.连续流动体系中负载型离子液体相（SILP）胺的烯丙基烷基化反应
ChemCatChem. 2023 Jun 22;15(12):e202300381. doi: 10.1002/cctc.202300381. Epub 2023 May 11.
2
Recent Advances in Enantioselective Pd-Catalyzed Allylic Substitution: From Design to Applications.对映选择性钯催化烯丙基取代反应的最新进展：从设计到应用
Chem Rev. 2021 Apr 28;121(8):4373-4505. doi: 10.1021/acs.chemrev.0c00736. Epub 2021 Mar 19.
3
Regio- and stereospecific rhodium-catalyzed allylic alkylation with an acyl anion equivalent: an approach to acyclic α-ternary β,γ-unsaturated aryl ketones.铑催化的区域和立体选择性烯丙基烷基化反应与酰基阴离子等价物：一种合成无环α-三元β，γ-不饱和芳基酮的方法。
Chem Sci. 2017 May 1;8(5):4001-4005. doi: 10.1039/c6sc05705e. Epub 2017 Mar 31.
4
Cu(II)-catalyzed aerobic hydroperoxidation of Meldrum's acid derivatives and application in intramolecular oxidation: a conceptual blueprint for O2/H2 dihydroxylation.Cu(II)催化的 Meldrum's 酸衍生物的有氧过氧氢化及在分子内氧化中的应用：O2/H2 双加氧反应的概念蓝图。
Org Lett. 2012 Dec 7;14(23):5932-5. doi: 10.1021/ol302848m. Epub 2012 Nov 19.
5
Palladium-catalyzed asymmetric allylic alkylation of electron-deficient pyrroles with meso electrophiles.钯催化的缺电子吡咯与内消旋亲电试剂的不对称烯丙基烷基化反应。
Org Lett. 2012 May 4;14(9):2254-7. doi: 10.1021/ol3006584. Epub 2012 Apr 16.
本文引用的文献
1
Synthesis of cyclopentitols by ring-closing approaches.通过闭环方法合成环戊糖醇。
Chem Rev. 2009 Dec;109(12):6809-57. doi: 10.1021/cr900169j.
2
Emerging of HIV drug resistance: epidemiology, diagnosis, treatment and prevention.HIV耐药性的出现：流行病学、诊断、治疗与预防
Curr HIV Res. 2009 May;7(3):273-8. doi: 10.2174/157016209788347976.
3
Pd(0)/InI-mediated allylic additions to 4-acetoxy-2-azetidinone: new route to highly functionalized carbocyclic scaffolds.钯(0)/碘化铟介导的4-乙酰氧基-2-氮杂环丁酮的烯丙基加成反应：通往高度官能化碳环骨架的新途径
Org Lett. 2009 Mar 19;11(6):1293-5. doi: 10.1021/ol9000685.
4
Asymmetric imino aza-enamine reaction catalyzed by axially chiral dicarboxylic acid: use of arylaldehyde N,N-dialkylhydrazones as acyl anion equivalent.轴手性二羧酸催化的不对称亚氨基氮杂烯胺反应：使用芳基醛N,N-二烷基腙作为酰基阴离子等价物。
J Am Chem Soc. 2008 Jun 18;130(24):7556-7. doi: 10.1021/ja802704j. Epub 2008 May 21.
5
Advances in acyl anion and homoenolate catalysis.酰基阴离子和同烯醇化物催化的进展。
Curr Opin Drug Discov Devel. 2007 Nov;10(6):691-703.
6
Predicting the stereochemistry of diphenylphosphino benzoic acid (DPPBA)-based palladium-catalyzed asymmetric allylic alkylation reactions: a working model.预测基于二苯基膦基苯甲酸（DPPBA）的钯催化不对称烯丙基烷基化反应的立体化学：一个工作模型。
Acc Chem Res. 2006 Oct;39(10):747-60. doi: 10.1021/ar040063c.
7
L-nucleoside enantiomers as antivirals drugs: a mini-review.L-核苷对映体作为抗病毒药物：一篇综述
Antiviral Res. 2006 Sep;71(2-3):276-81. doi: 10.1016/j.antiviral.2006.04.017. Epub 2006 May 23.
8
Zebularine: a new drug for epigenetic therapy.泽布勒林：一种用于表观遗传治疗的新药。
Biochem Soc Trans. 2004 Dec;32(Pt 6):910-2. doi: 10.1042/BST0320910.
9
Asymmetric allylic alkylation, an enabling methodology.不对称烯丙基烷基化，一种实用的方法。
J Org Chem. 2004 Sep 3;69(18):5813-37. doi: 10.1021/jo0491004.
10
Evolution of dithiane-based strategies for the construction of architecturally complex natural products.基于二硫烷构建结构复杂天然产物的策略的发展
Acc Chem Res. 2004 Jun;37(6):365-77. doi: 10.1021/ar030245r.
Zotero 插件