铱（I）催化的区域和对映选择性烯丙基酰胺化反应。
Iridium(I)-Catalyzed Regio- and Enantioselective Allylic Amidation.
作者信息
Singh Om V, Han Hyunsoo
机构信息
Department of Chemisry, The University of Texas at San Antonio, One UTSA Circle, San Antonio, TX 78249, USA.
出版信息
Tetrahedron Lett. 2007 Oct 1;48(40):7084-7098. doi: 10.1016/j.tetlet.2007.08.009.
Abstract
Ir(I)-catalyzed intermolecular allylic amidation of ethyl allylic carbonates with soft nitrogen nucleophiles under completely "salt-free" conditions is described. A combination of Ir(COD)Cl, a chiral phosphoramidite ligand L*, and DBU as a base in THF effects the reaction. The reaction appears to be quite general, accommodating a wide variety of R-groups and soft nitrogen nucleophiles, and proceeds with excellent regio- and enantioselectivities to afford the branched N-protected allylic amines. The developed reaction was conveniently utilized in the asymmetric synthesis of Boc protected alpha- and beta-amino acids as well as (-)-cytoxazone.
摘要
描述了在完全“无盐”条件下，铱（I）催化烯丙基碳酸乙酯与软质氮亲核试剂的分子间烯丙基酰胺化反应。[Ir(COD)Cl]₂、手性亚磷酰胺配体L*和DBU在四氢呋喃中作为碱的组合可实现该反应。该反应似乎具有相当的通用性，能兼容多种R基团和软质氮亲核试剂，并以优异的区域选择性和对映选择性进行反应，生成支链N-保护的烯丙基胺。所开发的反应可方便地用于Boc保护的α-和β-氨基酸以及（-）-细胞恶嗪的不对称合成。
相似文献
1
Iridium(I)-Catalyzed Regio- and Enantioselective Allylic Amidation.铱（I）催化的区域和对映选择性烯丙基酰胺化反应。
Tetrahedron Lett. 2007 Oct 1;48(40):7084-7098. doi: 10.1016/j.tetlet.2007.08.009.
2
Chiral Amines via Enantioselective π-Allyliridium-,-Benzoate-Catalyzed Allylic Alkylation: Student Training via Industrial-Academic Collaboration.手性胺的对映选择性π-烯丙基铱-，-苯甲酸酯催化的烯丙基烷基化：通过产学合作进行学生培训。
Acc Chem Res. 2022 Aug 2;55(15):2138-2147. doi: 10.1021/acs.accounts.2c00302. Epub 2022 Jul 13.
3
Iridium-catalyzed enantioselective allylic alkylation with functionalized organozinc bromides.铱催化的带有官能团的有机锌溴化物的对映选择性烯丙基烷基化反应。
Angew Chem Int Ed Engl. 2015 Jun 22;54(26):7644-7. doi: 10.1002/anie.201501851. Epub 2015 May 12.
4
Regio- and enantioselective iridium-catalyzed intermolecular allylic etherification of achiral allylic carbonates with phenoxides.铱催化的非手性烯丙基碳酸酯与酚盐的区域和对映选择性分子间烯丙基醚化反应
J Am Chem Soc. 2003 Mar 26;125(12):3426-7. doi: 10.1021/ja029790y.
5
Applications of Iridium-Catalyzed Asymmetric Allylic Substitution Reactions in Target-Oriented Synthesis.铱催化的不对称烯丙基取代反应在靶向合成中的应用。
Acc Chem Res. 2017 Oct 17;50(10):2539-2555. doi: 10.1021/acs.accounts.7b00300. Epub 2017 Sep 22.
6
Regio- and enantioselective allylic amination of achiral allylic esters catalyzed by an iridium-phosphoramidite complex.铱-亚磷酰胺配合物催化的非手性烯丙基酯的区域和对映选择性烯丙基胺化反应。
J Am Chem Soc. 2002 Dec 25;124(51):15164-5. doi: 10.1021/ja028614m.
7
Iridium-catalyzed regio- and enantioselective allylation of ketone enolates.铱催化酮烯醇盐的区域和对映选择性烯丙基化反应。
J Am Chem Soc. 2005 Dec 14;127(49):17192-3. doi: 10.1021/ja0566275.
8
Mechanistically driven development of iridium catalysts for asymmetric allylic substitution.基于机理的手性铱催化剂在不对称烯丙基取代反应中的发展。
Acc Chem Res. 2010 Dec 21;43(12):1461-75. doi: 10.1021/ar100047x. Epub 2010 Sep 28.
9
Direct, intermolecular, enantioselective, iridium-catalyzed allylation of carbamates to form carbamate-protected, branched allylic amines.铱催化的氨基甲酸酯直接、分子间、对映选择性烯丙基化反应，用于形成氨基甲酸酯保护的支链烯丙基胺。
Org Lett. 2009 Jul 2;11(13):2944-7. doi: 10.1021/ol901151u.
10
Palladium-Catalyzed Asymmetric Allylic C-H Functionalization: Mechanism, Stereo- and Regioselectivities, and Synthetic Applications.钯催化的不对称烯丙基 C-H 功能化：反应机理、立体和区域选择性及合成应用。
Acc Chem Res. 2020 Dec 15;53(12):2841-2854. doi: 10.1021/acs.accounts.0c00477. Epub 2020 Oct 2.
引用本文的文献
1
Synthesis Approaches to (-)-Cytoxazone, a Novel Cytokine Modulator, and Related Structures.新型细胞因子调节剂（-）-细胞恶唑酮及其相关结构的合成方法
Molecules. 2016 Sep 6;21(9):1176. doi: 10.3390/molecules21091176.
2
Mechanistically driven development of iridium catalysts for asymmetric allylic substitution.基于机理的手性铱催化剂在不对称烯丙基取代反应中的发展。
Acc Chem Res. 2010 Dec 21;43(12):1461-75. doi: 10.1021/ar100047x. Epub 2010 Sep 28.
本文引用的文献
1
Iridium-catalyzed, asymmetric amination of allylic alcohols activated by Lewis acids.铱催化的、由路易斯酸活化的烯丙醇的不对称胺化反应。
J Am Chem Soc. 2007 Jun 20;129(24):7508-9. doi: 10.1021/ja0730718. Epub 2007 May 25.
2
Iridium-catalysed asymmetric allylic substitutions.铱催化的不对称烯丙基取代反应。
Chem Commun (Camb). 2007 Feb 21(7):675-91. doi: 10.1039/b614169b. Epub 2006 Dec 6.
3
Iridium(I)-catalyzed regio- and enantioselective decarboxylative allylic amidation of substituted allyl benzyl imidodicarbonates.铱（I）催化取代烯丙基苄基亚胺二碳酸酯的区域和对映选择性脱羧烯丙基酰胺化反应
J Am Chem Soc. 2007 Jan 31;129(4):774-5. doi: 10.1021/ja067966g.
4
Salt-free iridium-catalyzed asymmetric allylic aminations with N,N-diacylamines and ortho-nosylamide as ammonia equivalents.以N,N-二酰基胺和邻位 nosylamide 作为氨等效物的无盐铱催化不对称烯丙基胺化反应
Angew Chem Int Ed Engl. 2006 Aug 18;45(33):5546-9. doi: 10.1002/anie.200601472.
5
Decarboxylative ring contractions and olefin insertions of vinyl oxazinanones.乙烯基恶唑烷酮的脱羧环收缩反应和烯烃插入反应
Org Lett. 2006 Jul 20;8(15):3211-4. doi: 10.1021/ol0610744.
6
Kinetic resolution of 2-oxazolidinones via catalytic, enantioselective N-acylation.通过催化对映选择性N-酰化实现2-恶唑烷酮的动力学拆分
J Am Chem Soc. 2006 May 24;128(20):6536-7. doi: 10.1021/ja061560m.
7
Phosphoramidite ligands in iridium-catalyzed allylic substitution.铱催化烯丙基取代反应中的亚磷酰胺配体
Chemistry. 2006 Apr 24;12(13):3596-609. doi: 10.1002/chem.200501180.
8
A simple iridium catalyst with a single resolved stereocenter for enantioselective allylic amination. Catalyst selection from mechanistic analysis.一种具有单一拆分立体中心的用于对映选择性烯丙基胺化反应的简单铱催化剂。基于机理分析的催化剂筛选。
J Am Chem Soc. 2005 Nov 9;127(44):15506-14. doi: 10.1021/ja054331t.
9
Highly enantioselective iridium-catalysed allylic aminations with anionic N-nucleophiles.铱催化的与阴离子型N-亲核试剂的高对映选择性烯丙基胺化反应
Chem Commun (Camb). 2005 Jul 28(28):3541-3. doi: 10.1039/b505197e. Epub 2005 Jun 9.
10
Kinetic study of various phosphoramidite ligands in the iridium-catalyzed allylic substitution.
Org Lett. 2005 Apr 14;7(8):1621-4. doi: 10.1021/ol050350w.
Zotero 插件