铑催化的炔烃与异氰酸酯的区域选择性分子间[2+2+2]环加成反应以形成吡啶酮。
Regioselective rhodium-catalyzed intermolecular [2+2+2] cycloaddition of alkynes and isocyanates to form pyridones.
作者信息
Oberg Kevin M, Lee Ernest E, Rovis Tomislav
机构信息
Department of Chemistry, Colorado State Univeristy, Fort Collins, CO 80523, USA.
出版信息
Tetrahedron. 2009 Jun 27;65(26):5056-5061. doi: 10.1016/j.tet.2009.02.021.
Abstract
A highly regioselective rhodium-catalyzed intermolecular [2+2+2] cycloaddition of terminal alkynes with a variety of isocyanates to provide 2- and 4-pyridones has been developed. This reaction proceeds in good to excellent yields and overcomes the problem of dimerization and trimerization through the use of phosphoramidite ligands. A CO migration in the metallacycle is proposed to account for the formation of 4-pyridone.
摘要
已开发出一种高度区域选择性的铑催化的末端炔烃与多种异氰酸酯的分子间[2+2+2]环加成反应，以提供2-吡啶酮和4-吡啶酮。该反应以良好至优异的产率进行，并通过使用亚磷酰胺配体克服了二聚化和三聚化问题。有人提出金属环中的CO迁移是4-吡啶酮形成的原因。
相似文献
1
Regioselective rhodium-catalyzed intermolecular [2+2+2] cycloaddition of alkynes and isocyanates to form pyridones.
Tetrahedron. 2009 Jun 27;65(26):5056-5061. doi: 10.1016/j.tet.2009.02.021.
2
Enantioselective rhodium-catalyzed [2 + 2 + 2] cycloadditions of terminal alkynes and alkenyl isocyanates: mechanistic insights lead to a unified model that rationalizes product selectivity.
J Am Chem Soc. 2009 Nov 4;131(43):15717-28. doi: 10.1021/ja905065j.
3
Enantioselective rhodium-catalyzed [2+2+2] cycloaddition of alkenyl isocyanates and terminal alkynes: application to the total synthesis of (+)-lasubine II.
J Am Chem Soc. 2006 Sep 27;128(38):12370-1. doi: 10.1021/ja064868m.
4
Phosphoramidite-Rhodium Complexes as Catalysts for the Asymmetric [2+2+2] Cycloaddition of Alkenyl Isocyanates and Alkynes.
Pure Appl Chem. 2009 Jul 1;82(7):1353-1364. doi: 10.1351/PAC-CON-09-12-09.
5
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.
6
Enantioselective synthesis of indolizidines bearing quaternary substituted stereocenters via rhodium-catalyzed [2+2+2] cycloaddition of alkenyl isocyanates and terminal alkynes.
Org Lett. 2008 Mar 20;10(6):1231-4. doi: 10.1021/ol800086s. Epub 2008 Feb 20.
7
Chemo- and regioselective intermolecular cyclotrimerization of terminal alkynes catalyzed by cationic rhodium(I)/modified BINAP complexes: application to one-step synthesis of paracyclophanes.
Chemistry. 2005 Feb 4;11(4):1145-56. doi: 10.1002/chem.200401017.
8
Rhodium-Catalyzed (5 + 2) and (5 + 1) Cycloadditions Using 1,4-Enynes as Five-Carbon Building Blocks.
Acc Chem Res. 2020 Jan 21;53(1):231-243. doi: 10.1021/acs.accounts.9b00477. Epub 2019 Dec 10.
9
Rhodium-catalyzed chemo-, regio-, and enantioselective [2 + 2 + 2] cycloaddition of alkynes with isocyanates.
Org Lett. 2005 Oct 13;7(21):4737-9. doi: 10.1021/ol052041b.
10
Enantioselective rhodium-catalyzed [4+2+2] cycloaddition of dienyl isocyanates for the synthesis of bicyclic azocine rings.
J Am Chem Soc. 2009 Sep 23;131(37):13250-1. doi: 10.1021/ja906641d.
引用本文的文献
1
Isocyanate-based multicomponent reactions.
RSC Adv. 2024 Dec 12;14(53):39253-39267. doi: 10.1039/d4ra04152f. eCollection 2024 Dec 10.
2
Rhodium-catalyzed asymmetric synthesis of silicon-stereogenic silicon-bridged arylpyridinones.
Chem Sci. 2016 Feb 1;7(2):1205-1211. doi: 10.1039/c5sc03767k. Epub 2015 Nov 9.
3
The iron-catalyzed construction of 2-aminopyrimidines from alkynenitriles and cyanamides.
Chem Commun (Camb). 2013 Sep 11;49(70):7735-7. doi: 10.1039/c3cc44422h.
4
Perfluorinated Taddol Phosphoramidite as an L,Z-Ligand on Rh(I) and Co(-I): Evidence for Bidentate Coordination via Metal-CF Interaction.
Chem Sci. 2013 May 1;4(5):2062-2070. doi: 10.1039/C3SC50271F.
5
Catalytic, asymmetric indolizidinone aza-quaternary stereocenter synthesis: expedient synthesis of the cylindricine alkaloid core.
Org Lett. 2013 May 17;15(10):2346-9. doi: 10.1021/ol400529k. Epub 2013 Apr 30.
6
Pyridine synthesis from oximes and alkynes via rhodium(III) catalysis: Cp* and Cp(t) provide complementary selectivity.
Chem Commun (Camb). 2011 Nov 21;47(43):11846-8. doi: 10.1039/c1cc15248c. Epub 2011 Oct 10.
7
Ni-catalyzed ketene cycloaddition: a system that resists the formation of decarbonylation side products.
J Am Chem Soc. 2011 May 25;133(20):7719-21. doi: 10.1021/ja2007627. Epub 2011 Apr 29.
8
Enantioselective rhodium-catalyzed [4+2] cycloaddition of α,β-unsaturated imines and isocyanates.
J Am Chem Soc. 2011 Apr 6;133(13):4785-7. doi: 10.1021/ja200766k. Epub 2011 Mar 14.
9
Phosphoramidite-Rhodium Complexes as Catalysts for the Asymmetric [2+2+2] Cycloaddition of Alkenyl Isocyanates and Alkynes.
Pure Appl Chem. 2009 Jul 1;82(7):1353-1364. doi: 10.1351/PAC-CON-09-12-09.
10
Multi-component cycloaddition approaches in the catalytic asymmetric synthesis of alkaloid targets.
Chem Soc Rev. 2009 Nov;38(11):3149-59. doi: 10.1039/b816702h. Epub 2009 Sep 15.
本文引用的文献
1
Asymmetric synthesis of bicyclic amidines via rhodium-catalyzed [2+2+2] cycloaddition of carbodiimides.
J Am Chem Soc. 2008 Mar 19;130(11):3262-3. doi: 10.1021/ja710065h. Epub 2008 Feb 27.
2
Enantioselective synthesis of indolizidines bearing quaternary substituted stereocenters via rhodium-catalyzed [2+2+2] cycloaddition of alkenyl isocyanates and terminal alkynes.
Org Lett. 2008 Mar 20;10(6):1231-4. doi: 10.1021/ol800086s. Epub 2008 Feb 20.
3
The fascinating construction of pyridine ring systems by transition metal-catalysed [2 + 2 + 2] cycloaddition reactions.
Chem Soc Rev. 2007 Jul;36(7):1085-94. doi: 10.1039/b607877j. Epub 2007 May 2.
4
High enantioselectivity is induced by a single monodentate phosphoramidite ligand in iridium-catalyzed asymmetric hydrogenation.
Angew Chem Int Ed Engl. 2007;46(9):1497-500. doi: 10.1002/anie.200603930.
5
Efficient synthesis of phenanthridinone derivatives via a palladium-catalyzed coupling process.
Org Lett. 2007 Jan 18;9(2):183-6. doi: 10.1021/ol062599z.
6
Enantioselective rhodium-catalyzed [2+2+2] cycloaddition of alkenyl isocyanates and terminal alkynes: application to the total synthesis of (+)-lasubine II.
J Am Chem Soc. 2006 Sep 27;128(38):12370-1. doi: 10.1021/ja064868m.
7
Rhodium-catalyzed [2 + 2 + 2] cycloaddition of alkenyl isocyanates and alkynes.
J Am Chem Soc. 2006 Mar 8;128(9):2782-3. doi: 10.1021/ja057803c.
8
Rhodium-catalyzed chemo-, regio-, and enantioselective [2 + 2 + 2] cycloaddition of alkynes with isocyanates.
Org Lett. 2005 Oct 13;7(21):4737-9. doi: 10.1021/ol052041b.
9
Bacterial topoisomerase inhibitors: quinolone and pyridone antibacterial agents.
Chem Rev. 2005 Feb;105(2):559-92. doi: 10.1021/cr030101q.
10
Cp*RuCl-catalyzed [2 + 2 + 2] cycloadditions of alpha,omega-diynes with electron-deficient carbon-heteroatom multiple bonds leading to heterocycles.
J Am Chem Soc. 2005 Jan 19;127(2):605-13. doi: 10.1021/ja045694g.
Zotero 插件