钯（0）催化的 N-烯丙基炔酰胺的氮杂-Claisen 重排和氮杂-Rautenstrauch 型环化的分歧机制途径。
A divergent mechanistic course of Pd(0)-catalyzed aza-Claisen rearrangement and aza-Rautenstrauch-type cyclization of N-allyl ynamides.
机构信息
Division of Pharmaceutical Sciences and Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53705, USA.
出版信息
Org Lett. 2010 Apr 16;12(8):1840-3. doi: 10.1021/ol100446p.
Abstract
A fascinating mechanistic study of ynamido-palladium-pi-allyl complexes is described that features isolation of a unique silyl ketenimine via aza-Claisen rearrangement, which can be accompanied by an unusual thermal N-to-C 1,3-Ts shift in the formation of tertiary nitriles and a novel cyclopentenimine formation via a palladium-catalyzed aza-Rautenstrauch-type cyclization pathway.
摘要
描述了一个关于ynamido-钯-π-烯丙基配合物的迷人的机理研究，该研究通过氮杂-Claisen 重排分离出独特的硅基烯酮亚胺，该重排可以伴随着一个不寻常的热 N 到 C 1,3-Ts 迁移，从而形成叔腈，以及通过钯催化的氮杂-Rautenstrauch 型环化途径形成新型环戊烯亚胺。
相似文献
1
A divergent mechanistic course of Pd(0)-catalyzed aza-Claisen rearrangement and aza-Rautenstrauch-type cyclization of N-allyl ynamides.
Org Lett. 2010 Apr 16;12(8):1840-3. doi: 10.1021/ol100446p.
2
Synthesis of cyclopentenimines from N-allyl ynamides via a tandem aza-Claisen rearrangement-carbocyclization sequence.
J Org Chem. 2013 Jun 21;78(12):6233-44. doi: 10.1021/jo400960e. Epub 2013 Jun 10.
3
Carbocyclization cascades of allyl ketenimines via aza-Claisen rearrangements of N-phosphoryl-N-allyl-ynamides.
Org Lett. 2012 Apr 6;14(7):1768-71. doi: 10.1021/ol300366e. Epub 2012 Mar 13.
4
An intramolecular [2 + 2] cycloaddition of ketenimines via palladium-catalyzed rearrangements of N-allyl-ynamides.
Org Lett. 2012 Jun 15;14(12):3214-7. doi: 10.1021/ol3013233. Epub 2012 Jun 5.
5
Pd-Catalyzed Rearrangement of -Alloc--allyl Ynamides Auto-Tandem Catalysis: Evidence for Reversible C-N Activation and Pd(0)-Accelerated Ketenimine Aza-Claisen Rearrangement.
Org Lett. 2021 Jan 15;23(2):559-564. doi: 10.1021/acs.orglett.0c04078. Epub 2021 Jan 7.
6
Synthesis of functionalized pyrroles via gold(I)-catalyzed aza-Claisen-type rearrangement.
Org Lett. 2007 Aug 2;9(16):3181-4. doi: 10.1021/ol0713032. Epub 2007 Jul 3.
7
Diastereoselective synthesis of anti-1,2-aminoalcohol by palladium(II) catalyzed aza-Claisen rearrangement.
Arch Pharm Res. 2004 Feb;27(2):136-42. doi: 10.1007/BF02980096.
8
Synthesis of polyfluoroalkyl cyclobutenes from 3-aza-1,5-enynes via an aza-Claisen rearrangement/cyclization cascade.
Org Lett. 2013 Sep 6;15(17):4512-5. doi: 10.1021/ol4020738. Epub 2013 Aug 22.
9
Synthesis of amidines using N-allyl ynamides. A palladium-catalyzed allyl transfer through an ynamido-pi-allyl complex.
Org Lett. 2009 Feb 19;11(4):899-902. doi: 10.1021/ol802844z.
10
Formation of substituted pyrroles via an imine condensation/Aza-Claisen rearrangement/imine-allene cyclization process by MAOS.
J Comb Chem. 2008 Jan-Feb;10(1):142-7. doi: 10.1021/cc700159u. Epub 2007 Dec 7.
引用本文的文献
1
PPh/Isocyanide and N/Isocyanide Exchange: Pathways to Isolable Alkali Metal Keteniminyl Anions.
Angew Chem Int Ed Engl. 2025 May;64(21):e202504325. doi: 10.1002/anie.202504325. Epub 2025 Mar 22.
2
Divergent C-H Insertion-Cyclization Cascades of N-Allyl Ynamides.
Angew Chem Int Ed Engl. 2015 Dec 14;54(51):15525-9. doi: 10.1002/anie.201507167. Epub 2015 Oct 30.
3
Ynamides in ring forming transformations.
Acc Chem Res. 2014 Feb 18;47(2):560-78. doi: 10.1021/ar400193g. Epub 2013 Oct 28.
4
A Convenient Synthesis of γ-Amino-Ynamides via Additions of Lithiated Ynamides to Aryl Imines. Observation of an -Meyer-Schuster Rearrangement.
Synthesis (Stuttg). 2013 Jul 1;45(13):1749-1758. doi: 10.1055/s-0033-1338476.
5
Synthesis of cyclopentenimines from N-allyl ynamides via a tandem aza-Claisen rearrangement-carbocyclization sequence.
J Org Chem. 2013 Jun 21;78(12):6233-44. doi: 10.1021/jo400960e. Epub 2013 Jun 10.
6
An intramolecular [2 + 2] cycloaddition of ketenimines via palladium-catalyzed rearrangements of N-allyl-ynamides.
Org Lett. 2012 Jun 15;14(12):3214-7. doi: 10.1021/ol3013233. Epub 2012 Jun 5.
7
Carbocyclization cascades of allyl ketenimines via aza-Claisen rearrangements of N-phosphoryl-N-allyl-ynamides.
Org Lett. 2012 Apr 6;14(7):1768-71. doi: 10.1021/ol300366e. Epub 2012 Mar 13.
8
Rhodium-catalyzed intra- and intermolecular [5 + 2] cycloaddition of 3-acyloxy-1,4-enyne and alkyne with concomitant 1,2-acyloxy migration.
J Am Chem Soc. 2012 Mar 21;134(11):5211-21. doi: 10.1021/ja2109097. Epub 2012 Mar 12.
9
Unexpected catalytic reactions of silyl-protected enol diazoacetates with nitrile oxides that form 5-arylaminofuran-2(3H)-one-4-carboxylates.
Org Lett. 2012 Feb 3;14(3):800-3. doi: 10.1021/ol203331r. Epub 2012 Jan 24.
10
A serendipitous discovery: nickel catalyst for the cycloaddition of diynes with unactivated nitriles.
Angew Chem Int Ed Engl. 2011 Nov 4;50(45):10694-8. doi: 10.1002/anie.201104475. Epub 2011 Sep 20.
本文引用的文献
1
A unique approach to aldol products for the creation of all-carbon quaternary stereocentres.
Nat Chem. 2009 May;1(2):128-32. doi: 10.1038/nchem.131. Epub 2009 Mar 29.
2
A Rhodium(I)-Xylyl-BINAP Catalyzed Asymmetric Ynamide-[2 + 2 + 2] Cycloaddition in the Synthesis of Optically Enriched N,O-Biaryls.
Tetrahedron. 2009 Jun 27;65(26):5001-5012. doi: 10.1016/j.tet.2009.03.078.
3
Enamine-iminium ion Nazarov cyclization of alpha-ketoenones.
Org Lett. 2010 Feb 5;12(3):440-3. doi: 10.1021/ol9025765.
4
Synthesis of ketene N,N-acetals by copper-catalyzed double-amidation of 1,1-dibromo-1-alkenes.
Org Lett. 2009 Oct 1;11(19):4454-7. doi: 10.1021/ol901831s.
5
Preparation of multisubstituted enamides via rhodium-catalyzed carbozincation and hydrozincation of ynamides.
J Org Chem. 2009 Oct 16;74(20):7849-58. doi: 10.1021/jo901658v.
6
Highly substituted 2-amido-furans from Rh(II)-catalyzed cyclopropenations of ynamides.
Org Lett. 2009 Oct 1;11(19):4462-5. doi: 10.1021/ol901860b.
7
Creating aldols differently: how to build up aldol products with quaternary stereocenters starting from alkynes.
Angew Chem Int Ed Engl. 2009;48(43):7971-3. doi: 10.1002/anie.200903773.
8
Highly regioselective Au(I)-catalyzed hydroamination of ynamides and propiolic acid derivatives with anilines.
Org Lett. 2009 Sep 17;11(18):4208-11. doi: 10.1021/ol901565p.
9
Ruthenium-catalyzed [2 + 2] cycloadditions of bicyclic alkenes with alkynyl phosphonates.
J Org Chem. 2009 Aug 7;74(15):5762-5. doi: 10.1021/jo9010206.
10
Predictable and regioselective insertion of internal unsymmetrical alkynes in rhodium-catalyzed cycloadditions with alkenyl isocyanates.
J Am Chem Soc. 2009 Aug 5;131(30):10775-82. doi: 10.1021/ja903899c.
Zotero 插件