双功能金鸡纳生物碱催化丙二酸酯与简单亚胺的曼尼希反应：β-氨基酸的对映选择性合成
The Mannich reaction of malonates with simple imines catalyzed by bifunctional cinchona alkaloids: enantioselective synthesis of beta-amino acids.
作者信息
Song Jun, Wang Yi, Deng Li
机构信息
Department of Chemistry, Brandeis University, Waltham, Massachusetts 02454-9110, USA.
出版信息
J Am Chem Soc. 2006 May 10;128(18):6048-9. doi: 10.1021/ja060716f.
Abstract
We describe the first efficient, direct asymmetric Mannich reactions with malonates and N-Boc aryl and alkyl imines by cooperative hydrogen-bonding catalysis with a cinchona alkaloid bearing a thiourea functionality. We have also extended the scope of this reaction to beta-ketoesters. The synthetic value of this new reaction is demonstrated in the establishment of a convergent enantioselective route toward the biologically important beta-amino acids under mild and air- and moisture-tolerant conditions.
摘要
我们描述了首例通过具有硫脲官能团的金鸡纳生物碱进行协同氢键催化，实现丙二酸酯与N - Boc芳基和烷基亚胺的高效、直接不对称曼尼希反应。我们还将该反应的适用范围扩展到了β - 酮酯。在温和且耐空气和湿气的条件下，通过建立一条汇聚式对映选择性路线来合成具有生物学重要性的β - 氨基酸，证明了这一新反应的合成价值。
相似文献
1
The Mannich reaction of malonates with simple imines catalyzed by bifunctional cinchona alkaloids: enantioselective synthesis of beta-amino acids.双功能金鸡纳生物碱催化丙二酸酯与简单亚胺的曼尼希反应：β-氨基酸的对映选择性合成
J Am Chem Soc. 2006 May 10;128(18):6048-9. doi: 10.1021/ja060716f.
2
Cooperative assistance in bifunctional organocatalysis: enantioselective Mannich reactions with aliphatic and aromatic imines.协同辅助双功能有机催化：脂肪族和芳香族亚胺的对映选择性曼尼希反应。
Angew Chem Int Ed Engl. 2012 Aug 20;51(34):8495-9. doi: 10.1002/anie.201203852. Epub 2012 Jul 9.
3
Direct enantio- and diastereoselective Mannich reactions of malonate and beta-keto esters with N-Boc and N-Cbz aldimines catalysed by a bifunctional cinchonine derivative.由双功能辛可宁衍生物催化的丙二酸酯和β-酮酯与N-Boc和N-Cbz醛亚胺的直接对映选择性和非对映选择性曼尼希反应。
Chem Commun (Camb). 2006 Mar 21(11):1191-3. doi: 10.1039/b515725k. Epub 2006 Feb 1.
4
Chiral calcium iodide for asymmetric Mannich-type reactions of malonates with imines providing β-aminocarbonyl compounds.手性碘化钙用于丙二酸盐与亚胺的不对称 Mannich 型反应，提供β-氨基羰基化合物。
Chem Asian J. 2013 May;8(5):872-6. doi: 10.1002/asia.201300102. Epub 2013 Mar 11.
5
Asymmetric Mannich reactions with in situ generation of carbamate-protected imines by an organic catalyst.通过有机催化剂原位生成氨基甲酸酯保护的亚胺的不对称曼尼希反应。
Org Lett. 2007 Feb 15;9(4):603-6. doi: 10.1021/ol062837q. Epub 2007 Jan 27.
6
Organocatalytic enantioselective decarboxylative reaction of malonic acid half thioesters with cyclic N-sulfonyl ketimines by using N-heteroarenesulfonyl cinchona alkaloid amides.通过使用氮杂芳基磺酰基金鸡纳生物碱酰胺实现丙二酸半硫酯与环状N-磺酰基酮亚胺的有机催化对映选择性脱羧反应。
Chemistry. 2015 Mar 2;21(10):3929-32. doi: 10.1002/chem.201406270. Epub 2015 Jan 22.
7
Diastereo- and enantioselective nitro-Mannich reaction of α-substituted nitroacetates to N-phosphoryl imines catalyzed by cinchona alkaloid thiourea organocatalysts.手性金鸡纳生物碱硫脲有机催化剂催化的α-取代硝基乙酸酯的非对映选择性和对映选择性硝-曼尼希反应与 N-膦酰亚胺。
Org Biomol Chem. 2013 May 21;11(19):3223-9. doi: 10.1039/c3ob40335a. Epub 2013 Apr 12.
8
Synthesis of α-amino acid derivatives and peptides via enantioselective addition of masked acyl cyanides to imines.通过将掩蔽的酰基氰化物对亚胺进行对映选择性加成来合成α-氨基酸衍生物和肽。
J Am Chem Soc. 2014 Nov 19;136(46):16148-51. doi: 10.1021/ja510135t. Epub 2014 Nov 7.
9
Asymmetric Mannich reactions of beta-keto esters with acyl imines catalyzed by cinchona alkaloids.金鸡纳生物碱催化的β-酮酯与酰基亚胺的不对称曼尼希反应。
J Am Chem Soc. 2005 Aug 17;127(32):11256-7. doi: 10.1021/ja0537373.
10
Highly enantio- and diastereoselective Mannich reactions of glycine Schiff bases with in situ generated N-Boc-imines catalyzed by a cinchona alkaloid thiourea.高对映选择性和非对映选择性的甘氨酸席夫碱与原位生成的 N-Boc-亚胺的曼尼希反应，由金鸡纳生物碱硫脲催化。
Org Lett. 2010 Feb 19;12(4):708-11. doi: 10.1021/ol902722y.
引用本文的文献
1
Organocatalytic Enantioselective γ-Position-Selective Mannich Reactions of β-Ketocarbonyl Derivatives.β-酮羰基衍生物的有机催化对映选择性γ-位选择性曼尼希反应
Org Lett. 2022 Sep 23;24(37):6711-6715. doi: 10.1021/acs.orglett.2c02433. Epub 2022 Sep 12.
2
BIMP-Catalyzed 1,3-Prototropic Shift for the Highly Enantioselective Synthesis of Conjugated Cyclohexenones.BIMP 催化的 1,3-质子迁移反应在手性共轭环己烯酮的高对映选择性合成中的应用。
Angew Chem Int Ed Engl. 2020 Sep 28;59(40):17417-17422. doi: 10.1002/anie.202006202. Epub 2020 Aug 7.
3
First Organocatalytic Asymmetric Synthesis of 1-Benzamido-1,4-Dihydropyridine Derivatives.首例手性有机催化 1-苯甲酰胺基-1,4-二氢吡啶衍生物的不对称合成。
Molecules. 2018 Oct 19;23(10):2692. doi: 10.3390/molecules23102692.
4
Novel amide-functionalized chloramphenicol base bifunctional organocatalysts for enantioselective alcoholysis of -cyclic anhydrides.用于环酐对映选择性醇解的新型酰胺官能化氯霉素碱双功能有机催化剂。
Beilstein J Org Chem. 2018 Jan 31;14:309-317. doi: 10.3762/bjoc.14.19. eCollection 2018.
5
Room-temperature enantioselective C-H iodination via kinetic resolution.室温下通过动力学拆分实现对映选择性 C-H 碘化反应。
Science. 2014 Oct 24;346(6208):451-5. doi: 10.1126/science.1258538.
6
Silyl imine electrophiles in enantioselective catalysis: a Rosetta Stone for peptide homologation, enabling diverse N-protected aryl glycines from aldehydes in three steps.手性催化中的硅亚胺亲电试剂：多肽同系化的罗塞塔石，可通过三步法从醛制备各种 N-保护芳基甘氨酸。
Org Lett. 2014 Jun 6;16(11):3146-9. doi: 10.1021/ol501297a. Epub 2014 May 14.
7
Cinchona alkaloid derivative-catalyzed enantioselective synthesis via a Mannich-type reaction and antifungal activity of β-amino esters bearing benzoheterocycle moieties.金鸡纳生物碱衍生物催化的通过曼尼希型反应的对映选择性合成以及含苯并杂环部分的β-氨基酯的抗真菌活性。
Molecules. 2014 Apr 1;19(4):3955-72. doi: 10.3390/molecules19043955.
8
Bifunctional cinchona alkaloid-squaramide-catalyzed highly enantioselective aza-Michael addition of indolines to α,β-unsaturated ketones.双功能金鸡纳生物碱-方酰胺催化二氢吲哚对α,β-不饱和酮的高对映选择性氮杂-Michael加成反应。
Tetrahedron Lett. 2013 Jul 3;54(27):3500-3502. doi: 10.1016/j.tetlet.2013.04.080.
9
Nitrogen-containing apigenin analogs: preparation and biological activity.含氮芹菜素类似物的制备及生物活性。
Molecules. 2012 Dec 11;17(12):14748-64. doi: 10.3390/molecules171214748.
10
Highly enantioselective three-component direct Mannich reactions of unfunctionalized ketones catalyzed by bifunctional organocatalysts.双功能有机催化剂催化的未功能化酮的高对映选择性三组分直接曼尼希反应。
Org Lett. 2013 Feb 1;15(3):508-11. doi: 10.1021/ol303315c. Epub 2013 Jan 23.
本文引用的文献
1
Direct enantio- and diastereoselective Mannich reactions of malonate and beta-keto esters with N-Boc and N-Cbz aldimines catalysed by a bifunctional cinchonine derivative.由双功能辛可宁衍生物催化的丙二酸酯和β-酮酯与N-Boc和N-Cbz醛亚胺的直接对映选择性和非对映选择性曼尼希反应。
Chem Commun (Camb). 2006 Mar 21(11):1191-3. doi: 10.1039/b515725k. Epub 2006 Feb 1.
2
A direct catalytic asymmetric Mannich-type reaction via a dinuclear zinc catalyst: synthesis of either anti- or syn-alpha-hydroxy-beta-amino ketones.通过双核锌催化剂实现的直接催化不对称曼尼希型反应：抗式或顺式α-羟基-β-氨基酮的合成。
J Am Chem Soc. 2006 Mar 8;128(9):2778-9. doi: 10.1021/ja057498v.
3
Direct asymmetric anti-Mannich-type reactions catalyzed by a designed amino acid.由一种设计的氨基酸催化的直接不对称抗曼尼希型反应。
J Am Chem Soc. 2006 Feb 1;128(4):1040-1. doi: 10.1021/ja056984f.
4
Enantioselective nitroaldol reaction of alpha-ketoesters catalyzed by cinchona alkaloids.金鸡纳生物碱催化的α-酮酯对映选择性硝基羟醛反应。
J Am Chem Soc. 2006 Jan 25;128(3):732-3. doi: 10.1021/ja057237l.
5
Construction of quaternary stereocenters by efficient and practical conjugate additions to alpha,beta-unsaturated ketones with a chiral organic catalyst.通过手性有机催化剂对α,β-不饱和酮进行高效且实用的共轭加成反应构建季碳立体中心。
Angew Chem Int Ed Engl. 2006 Jan 30;45(6):947-50. doi: 10.1002/anie.200502658.
6
anti-selective direct asymmetric Mannich reactions catalyzed by axially chiral amino sulfonamide as an organocatalyst.轴手性氨基磺酰胺作为有机催化剂催化的反选择性直接不对称曼尼希反应。
J Am Chem Soc. 2005 Nov 30;127(47):16408-9. doi: 10.1021/ja056008w.
7
Kinetic resolution of oxazinones: an organocatalytic approach to enantiomerically pure beta-amino acids.恶唑烷酮的动力学拆分：一种制备对映体纯β-氨基酸的有机催化方法。
Angew Chem Int Ed Engl. 2005 Dec 1;44(45):7466-9. doi: 10.1002/anie.200502003.
8
Bifunctional-thiourea-catalyzed diastereo- and enantioselective aza-Henry reaction.双功能硫脲催化的非对映和对映选择性氮杂-Henry反应
Chemistry. 2005 Dec 23;12(2):466-76. doi: 10.1002/chem.200500735.
9
Urea- and thiourea-substituted cinchona alkaloid derivatives as highly efficient bifunctional organocatalysts for the asymmetric addition of malonate to nitroalkenes: inversion of configuration at C9 dramatically improves catalyst performance.尿素和硫脲取代的金鸡纳生物碱衍生物作为丙二酸酯对硝基烯烃不对称加成反应的高效双功能有机催化剂：C9位构型翻转显著提高催化剂性能。
Angew Chem Int Ed Engl. 2005 Oct 7;44(39):6367-70. doi: 10.1002/anie.200501721.
10
Enantioselective organocatalytic Michael addition of malonate esters to nitro olefins using bifunctional cinchonine derivatives.使用双功能辛可宁衍生物实现丙二酸酯对硝基烯烃的对映选择性有机催化迈克尔加成反应。
Chem Commun (Camb). 2005 Sep 21(35):4481-3. doi: 10.1039/b508833j. Epub 2005 Aug 8.
Zotero 插件