膦催化的亲核试剂对活化的α-烷基丙二烯的β'-Umpolung 加成反应。
Phosphine-catalyzed β'-umpolung addition of nucleophiles to activated α-alkyl allenes.
机构信息
Department of Chemistry and Biochemistry, University of California, Los Angeles, Los Angeles, California 90095-1569, United States.
出版信息
Org Lett. 2011 May 20;13(10):2586-9. doi: 10.1021/ol200697m. Epub 2011 Apr 14.
Abstract
Highly functionalized alkenes can be prepared through phosphine-catalyzed β'-umpolung additions of nucleophiles (carbon-, oxygen-, nitrogen-, and sulfur-centered) to activated α-disubstituted allenes, providing many potentially useful synthetic intermediates in good to excellent yields, often with high levels of stereoselectivity for the product olefin geometry. Various substitution patterns around the allene are compatible with the process, showcasing the synthetic utility of allenes under the conditions of nucleophilic phosphine catalysis.
摘要
高功能化的烯烃可以通过膦催化的亲核试剂（碳、氧、氮和硫中心）对活化的α-二取代烯丙基的β'-反转加成来制备，以良好至优异的收率提供许多潜在有用的合成中间体，通常产物烯烃几何形状的立体选择性很高。烯丙基周围的各种取代模式与该过程兼容，展示了在亲核膦催化条件下烯丙基的合成实用性。
相似文献
1
Phosphine-catalyzed β'-umpolung addition of nucleophiles to activated α-alkyl allenes.
Org Lett. 2011 May 20;13(10):2586-9. doi: 10.1021/ol200697m. Epub 2011 Apr 14.
2
Advances in nucleophilic phosphine catalysis of alkenes, allenes, alkynes, and MBHADs.
Chem Commun (Camb). 2013 Dec 25;49(99):11588-619. doi: 10.1039/c3cc47368f.
3
Phosphine-catalyzed [4+2] annulations of 2-alkylallenoates and olefins: synthesis of multisubstituted cyclohexenes.
Chem Asian J. 2011 Aug 1;6(8):2101-6. doi: 10.1002/asia.201100190. Epub 2011 Jul 7.
4
Phosphine-catalyzed enantioselective intramolecular [3+2] annulations to generate fused ring systems.
J Am Chem Soc. 2015 Apr 8;137(13):4587-91. doi: 10.1021/jacs.5b01985. Epub 2015 Mar 27.
5
Phosphine-Mediated Iterative Arene Homologation Using Allenes.
J Am Chem Soc. 2015 Sep 9;137(35):11258-61. doi: 10.1021/jacs.5b07403. Epub 2015 Aug 31.
6
Phosphine Organocatalysis.
Chem Rev. 2018 Oct 24;118(20):10049-10293. doi: 10.1021/acs.chemrev.8b00081. Epub 2018 Sep 27.
7
Phosphine catalysis of allenes with electrophiles.
Chem Soc Rev. 2014 May 7;43(9):2927-40. doi: 10.1039/c4cs00054d. Epub 2014 Mar 24.
8
Phosphine-initiated general base catalysis: facile access to benzannulated 1,3-diheteroatom five-membered rings via double-Michael reactions of allenes.
Org Lett. 2011 Oct 21;13(20):5420-3. doi: 10.1021/ol201730q. Epub 2011 Sep 20.
9
Enantioselective Synthesis of Spirobarbiturate-Cyclohexenes through Phosphine-Catalyzed Asymmetric [4 + 2] Annulation of Barbiturate-Derived Alkenes with Allenoates.
Org Lett. 2016 Mar 18;18(6):1302-5. doi: 10.1021/acs.orglett.6b00239. Epub 2016 Mar 3.
10
Phosphine-catalyzed formation of carbon-sulfur bonds: catalytic asymmetric synthesis of gamma-thioesters.
J Am Chem Soc. 2010 Apr 7;132(13):4568-9. doi: 10.1021/ja101251d.
引用本文的文献
1
Synthesis of 3,4-Disubstituted Maleimide Derivatives via Phosphine-Catalyzed Isomerization of α-Succinimide-Substituted Allenoates Cascade γ'-Addition with Aryl Imines.
Int J Mol Sci. 2024 Jun 24;25(13):6916. doi: 10.3390/ijms25136916.
2
Quick construction of a C-N bond from arylsulfonyl hydrazides and C-X compounds promoted by DMAP at room temperature.
RSC Adv. 2019 Jun 26;9(35):19917-19923. doi: 10.1039/c9ra03403j. eCollection 2019 Jun 25.
3
Phosphine-Catalyzed (4+1) Annulation: Rearrangement of Allenylic Carbamates to 3-Pyrrolines through Phosphonium Diene Intermediates.
ChemCatChem. 2020 Sep 4;12(17):4352-4372. doi: 10.1002/cctc.202000626. Epub 2020 May 22.
4
Phosphine Organocatalysis.
Chem Rev. 2018 Oct 24;118(20):10049-10293. doi: 10.1021/acs.chemrev.8b00081. Epub 2018 Sep 27.
5
Reaction of allene esters with Selectfluor/TMSX (X = I, Br, Cl) and Selectfluor/NH4SCN: Competing oxidative/electrophilic dihalogenation and nucleophilic/conjugate addition.
Beilstein J Org Chem. 2015 Sep 16;11:1641-8. doi: 10.3762/bjoc.11.180. eCollection 2015.
6
Stereoselective Syntheses of α,β-Unsaturated γ-Amino Esters Through Phosphine-Catalyzed γ-Umpolung Additions of Sulfonamides to γ-Substituted Allenoates.
Tetrahedron Lett. 2015 Jun 3;56(23):3273-3276. doi: 10.1016/j.tetlet.2015.01.120.
7
Advances in nucleophilic phosphine catalysis of alkenes, allenes, alkynes, and MBHADs.
Chem Commun (Camb). 2013 Dec 25;49(99):11588-619. doi: 10.1039/c3cc47368f.
8
Phosphine-catalyzed intramolecular γ-umpolung addition of α-aminoalkylallenic esters: facile synthesis of 3-carbethoxy-2-alkyl-3-pyrrolines.
Chem Commun (Camb). 2012 May 28;48(43):5373-5. doi: 10.1039/c2cc31347b. Epub 2012 Apr 23.
9
Phosphine-initiated general base catalysis: facile access to benzannulated 1,3-diheteroatom five-membered rings via double-Michael reactions of allenes.
Org Lett. 2011 Oct 21;13(20):5420-3. doi: 10.1021/ol201730q. Epub 2011 Sep 20.
10
Diversity-oriented synthesis based on the DPPP-catalyzed mixed double-Michael reactions of electron-deficient acetylenes and β-amino alcohols.
Molecules. 2011 May 5;16(5):3802-25. doi: 10.3390/molecules16053802.
本文引用的文献
1
Equilibrium between a vinylogous ylide and a phosphonium dienolate zwitterion: vinylogous Wittig olefination versus vinylogous aldol-type reaction.
Tetrahedron. 2010 Jun;66(26):4760-4768. doi: 10.1016/j.tet.2010.03.044.
2
Phosphine-catalyzed tandem reaction of allenoates with nitroalkenes.
Org Lett. 2010 Nov 5;12(21):5024-7. doi: 10.1021/ol102191p.
3
Diastereoselective synthesis of 6-trifluoromethyl-5,6-dihydropyrans via phosphine-catalyzed [4 + 2] annulation of α-benzylallenoates with ketones.
Org Lett. 2010 Sep 17;12(18):4168-71. doi: 10.1021/ol101762z.
4
Carbon-carbon bond formation and pyrrole synthesis via the [3,3] sigmatropic rearrangement of O-vinyl oxime ethers.
Org Lett. 2010 May 21;12(10):2290-3. doi: 10.1021/ol100659q.
5
PHOSPHINE-CATALYZED [4+2] ANNULATION: SYNTHESIS OF ETHYL 6-PHENYL-1-TOSYL-1,2,5,6-TETRAHYDROPYRIDINE-3-CARBOXYLATE.
Organic Synth. 2009 Mar 1;2009(86):212-224. doi: 10.1002/0471264229.os086.21.
6
2-(Acetoxymethyl)buta-2,3-dienoate, a versatile 1,4-biselectrophile for phosphine-catalyzed (4 + n) annulations with 1,n-Bisnucleophiles (n = 1, 2).
J Am Chem Soc. 2010 Mar 3;132(8):2550-1. doi: 10.1021/ja100432m.
7
Enantioselective catalysis and complexity generation from allenoates.
Chem Soc Rev. 2009 Nov;38(11):3102-16. doi: 10.1039/b816700c. Epub 2009 Jul 24.
8
Asymmetric carbon-carbon bond formation gamma to a carbonyl group: phosphine-catalyzed addition of nitromethane to allenes.
J Am Chem Soc. 2009 Oct 14;131(40):14231-3. doi: 10.1021/ja9061823.
9
Phosphine-promoted [3 + 3] annulations of aziridines with allenoates: facile entry into highly functionalized tetrahydropyridines.
J Am Chem Soc. 2009 May 13;131(18):6318-9. doi: 10.1021/ja8097349.
10
Phosphine-catalyzed enantioselective synthesis of oxygen heterocycles.
Angew Chem Int Ed Engl. 2009;48(12):2225-7. doi: 10.1002/anie.200805377.
Zotero 插件