使用串联迈克尔 - 亨利反应对双环[3.2.1]辛烷 - 8 - 酮进行对映选择性合成。
Enantioselective synthesis of bicylco[3.2.1]octan-8-ones using a tandem Michael-Henry reaction.
作者信息
Ding Derong, Zhao Cong-Gui, Guo Qunsheng, Arman Hadi
机构信息
Department of Chemistry, University of Texas at San Antonio, One UTSA Circle, San Antonio, Texas 78249-0698, USA.
出版信息
Tetrahedron. 2010 Jun 19;66(25):4423-4427. doi: 10.1016/j.tet.2010.04.044.
Abstract
Bicyclo[3.2.1]octan-8-ones have been prepared from a tandem Michael-Henry reaction between cyclohexane-1,2-diones and nitroalkenes using a quinine-derived thiourea as the catalyst. Although four stereogenic centers were created during the reaction, only two diastereomers were obtained in good diastereoselectivity and high enantioselectivity (92-99% ee). When 3-methylcyclohexane-1,2-dione (R(1) = Me) was used as the substrate, only the regioisomeric product of the corresponding thermodynamic enolate was obtained.
摘要
双环[3.2.1]辛烷-8-酮是通过环己烷-1,2-二酮与硝基烯烃之间的串联迈克尔-亨利反应制备的，使用奎宁衍生的硫脲作为催化剂。尽管反应过程中产生了四个立体中心，但仅以良好的非对映选择性和高对映选择性（对映体过量92-99%）得到了两种非对映异构体。当使用3-甲基环己烷-1,2-二酮（R(1) = 甲基）作为底物时，仅得到了相应热力学烯醇盐的区域异构体产物。
相似文献
1
Enantioselective synthesis of bicylco[3.2.1]octan-8-ones using a tandem Michael-Henry reaction.
Tetrahedron. 2010 Jun 19;66(25):4423-4427. doi: 10.1016/j.tet.2010.04.044.
2
Organocatalytic asymmetric domino Michael-Henry reaction for the synthesis of substituted bicyclo[3.2.1]octan-2-ones.
Chem Commun (Camb). 2013 Mar 18;49(22):2219-21. doi: 10.1039/c3cc39165e.
3
Organocatalytic Enantioselective Synthesis of Tetrahydrofluoren-9-ones via Vinylogous Michael Addition/Henry Reaction Cascade of 1,3-Indandione-Derived Pronucleophiles.
Org Lett. 2016 Feb 19;18(4):688-91. doi: 10.1021/acs.orglett.5b03663. Epub 2016 Feb 3.
4
Organocatalytic Enantioselective Michael-Michael-Henry Reaction Cascade. An Entry to Highly Functionalized Hajos-Parrish-Type Ketones with Five to Six Contiguous Stereogenic Centers and Two Quaternary Carbons.
Org Lett. 2016 Apr 15;18(8):1760-3. doi: 10.1021/acs.orglett.6b00459. Epub 2016 Mar 28.
5
Highly diastereo- and enantioselective organocatalytic michael addition of α-ketoamides to nitroalkenes.
Org Lett. 2010 Nov 19;12(22):5246-9. doi: 10.1021/ol102289g. Epub 2010 Oct 25.
6
New approach to the preparation of bicyclo octane derivatives via the enantioselective cascade reaction catalyzed by chiral diamine-Ni(OAc)2 complex.
Org Biomol Chem. 2012 Jun 28;10(24):4767-73. doi: 10.1039/c2ob25135c. Epub 2012 May 16.
7
Synthesis of non-racemic 4-nitro-2-sulfonylbutan-1-ones via Ni(II)-catalyzed asymmetric Michael reaction of β-ketosulfones.
Beilstein J Org Chem. 2019 Jun 12;15:1289-1297. doi: 10.3762/bjoc.15.127. eCollection 2019.
8
Organocatalytic Asymmetric Domino Michael/Henry Reaction of Indolin-3-ones with -Formyl-β-nitrostyrenes.
Synthesis (Stuttg). 2015 Apr 1;47(7):1024-1031. doi: 10.1055/s-0034-1379943.
9
One-pot sequential organocatalysis: highly stereoselective synthesis of trisubstituted cyclohexanols.
Chemistry. 2013 Jan 28;19(5):1666-71. doi: 10.1002/chem.201203104. Epub 2012 Dec 13.
10
Diastereo- and enantioselective Aza-MBH-type reaction of nitroalkenes to N-tosylimines catalyzed by bifunctional organocatalysts.
Org Lett. 2009 Aug 6;11(15):3310-3. doi: 10.1021/ol9011458.
引用本文的文献
1
Enantioselective synthesis of bicyclo[3.n.1]alkanes by chiral phosphoric acid-catalyzed desymmetrizing Michael cyclizations.
Chem Sci. 2015 Jun 1;6(6):3550-3555. doi: 10.1039/c5sc00753d. Epub 2015 Apr 30.
2
Anion-π catalysis: bicyclic products with four contiguous stereogenic centers from otherwise elusive diastereospecific domino reactions on π-acidic surfaces.
Chem Sci. 2017 May 1;8(5):3770-3774. doi: 10.1039/c7sc00525c. Epub 2017 Mar 17.
3
(Thio)urea-mediated synthesis of functionalized six-membered rings with multiple chiral centers.
Beilstein J Org Chem. 2016 Mar 10;12:462-95. doi: 10.3762/bjoc.12.48. eCollection 2016.
4
Organocatalyzed asymmetric Michael reaction of β-aryl-α-ketophosphonates and nitroalkenes.
Tetrahedron Lett. 2013 Oct 16;54(42). doi: 10.1016/j.tetlet.2013.08.015.
5
Organocatalytic enantioselective tandem aldol-cyclization reaction of α-isothiocyanato imides and activated carbonyl compounds.
Tetrahedron Asymmetry. 2011 Jun 15;22(11):1205-1211. doi: 10.1016/j.tetasy.2011.06.028.
6
Developing novel organocatalyzed aldol reactions for the enantioselective synthesis of biologically active molecules.
Synthesis (Stuttg). 2011 Jun;2011(12):1815-1830. doi: 10.1055/s-0030-1260029.
本文引用的文献
1
Organocatalyzed synthesis of 2-amino-8-oxo-5,6,7,8-tetrahydro-4H-chromene-3-carbonitriles.
Tetrahedron Lett. 2010 Mar 3;51(9):1322. doi: 10.1016/j.tetlet.2009.12.139.
2
Synthesis of 2,3,4-Trisubstituted Thiochromanes using an Organocatalytic Enantioselective Tandem Michael-Henry Reaction.
Adv Synth Catal. 2008 Feb 26;350(4):537-541. doi: 10.1002/adsc.200700331.
3
One-pot synthesis of pentasubstituted cyclohexanes by a Michael addition followed by a tandem inter-intra double Henry reaction.
Chemistry. 2009 Jul 6;15(27):6576-80. doi: 10.1002/chem.200900894.
4
Asymmetric organocatalytic domino Michael/aldol reactions: enantioselective synthesis of chiral cycloheptanones, tetrahydrochromenones, and polyfunctionalized bicyclo[3.2.1]octanes.
Angew Chem Int Ed Engl. 2009;48(20):3699-702. doi: 10.1002/anie.200900754.
5
Organocatalytic Highly Enantioselective Tandem Michael-Knoevenagel Reaction for the Synthesis of Substituted Thiochromanes.
Tetrahedron Lett. 2008 Mar 17;49(12):1899-1902. doi: 10.1016/j.tetlet.2008.01.113.
6
Stereocontrolled synthesis of fully functionalized D-glucosamine monosaccharides via a domino nitro-Michael/Henry reaction.
Chem Commun (Camb). 2008 Aug 14(30):3549-51. doi: 10.1039/b805159c. Epub 2008 Jun 4.
7
A highly diastereo- and enantioselective synthesis of multisubstituted cyclopentanes with four chiral carbons by the organocatalytic domino Michael-Henry reaction.
Org Lett. 2008 Aug 21;10(16):3489-92. doi: 10.1021/ol801273x. Epub 2008 Jul 17.
8
Control of four stereocenters in an organocatalytic domino double Michael reaction: efficient synthesis of multisubstituted cyclopentanes.
Org Lett. 2008 Aug 21;10(16):3425-8. doi: 10.1021/ol801246m. Epub 2008 Jul 11.
9
Organocatalytic asymmetric tandem Michael-Henry reactions: a highly stereoselective synthesis of multifunctionalized cyclohexanes with two quaternary stereocenters.
Org Lett. 2008 Jun 19;10(12):2437-40. doi: 10.1021/ol8007183. Epub 2008 May 20.
10
Microwave-accelerated spiro-cyclizations of o-halobenzyl cyclohexenyl ethers by palladium(0) catalysis.
J Org Chem. 2007 Jul 20;72(15):5851-4. doi: 10.1021/jo0708487. Epub 2007 Jun 28.
Zotero 插件