钯催化的烯烃分子间氨乙酰氧基化反应和 PhI(OAc)2 对氨钯化立体选择性的影响。
Palladium-catalyzed intermolecular aminoacetoxylation of alkenes and the influence of PhI(OAc)2 on aminopalladation stereoselectivity.
机构信息
Institute of Chemical Research of Catalonia (ICIQ), 43007 Tarragona, Spain.
出版信息
J Org Chem. 2013 Jun 21;78(12):6309-15. doi: 10.1021/jo400671q. Epub 2013 Jun 4.
Abstract
A modified protocol has been identified for Pd-catalyzed intermolecular aminoacetoxylation of terminal and internal alkenes that enables the alkene to be used as the limiting reagent. The results prompt a reassessment of the stereochemical course of these reactions. X-ray crystallographic characterization of two of the products, together with isotopic labeling studies, show that the amidopalladation step switches from a cis-selective process under aerobic conditions to a trans-selective process in the presence of diacetoxyiodobenzene.
摘要
已确定一种用于 Pd 催化的末端和内部烯烃的氨基乙氧羰基化的改进方案，该方案可以使烯烃成为限制试剂。结果促使对这些反应的立体化学过程进行重新评估。通过对两个产物的 X 射线晶体学表征以及同位素标记研究，表明在有氧条件下，酰胺钯化步骤由顺式选择性过程转变为在二醋酸碘苯存在下的反式选择性过程。
相似文献
1
Palladium-catalyzed intermolecular aminoacetoxylation of alkenes and the influence of PhI(OAc)2 on aminopalladation stereoselectivity.钯催化的烯烃分子间氨乙酰氧基化反应和 PhI(OAc)2 对氨钯化立体选择性的影响。
J Org Chem. 2013 Jun 21;78(12):6309-15. doi: 10.1021/jo400671q. Epub 2013 Jun 4.
2
Highly regioselective Pd-catalyzed intermolecular aminoacetoxylation of alkenes and evidence for cis-aminopalladation and S(N)2 C-O bond formation.钯催化的烯烃分子间氨基乙酰氧基化反应具有高度区域选择性以及顺式氨基钯化和S(N)2 C-O键形成的证据。
J Am Chem Soc. 2006 Jun 7;128(22):7179-81. doi: 10.1021/ja061706h.
3
Palladium-catalyzed aerobic oxidative amination of alkenes: development of intra- and intermolecular aza-Wacker reactions.钯催化的烯烃需氧氧化胺化反应：分子内和分子间氮杂瓦克反应的发展
Inorg Chem. 2007 Mar 19;46(6):1910-23. doi: 10.1021/ic061997v.
4
Palladium-catalyzed ring-forming aminoacetoxylation of alkenes.钯催化的烯烃成环氨基乙酰氧基化反应。
J Am Chem Soc. 2005 Jun 1;127(21):7690-1. doi: 10.1021/ja051406k.
5
Two-faced reactivity of alkenes: cis- versus trans-aminopalladation in aerobic Pd-catalyzed intramolecular aza-Wacker reactions.烯烃的双面反应性：有氧钯催化分子内氮杂瓦克反应中的顺式与反式氨基钯化反应
J Am Chem Soc. 2007 May 16;129(19):6328-35. doi: 10.1021/ja070424u. Epub 2007 Apr 18.
6
Mechanistic studies of Wacker-type amidocyclization of alkenes catalyzed by (IMes)Pd(TFA)2(H2O): kinetic and stereochemical implications of proton transfer.（IMes）Pd（TFA）2（H2O）催化的 Wacker 型烯烃酰胺环化反应的机理研究：质子转移的动力学和立体化学意义。
J Org Chem. 2013 Mar 1;78(5):2083-90. doi: 10.1021/jo302266t. Epub 2012 Nov 30.
7
Influence of catalyst structure and reaction conditions on anti- versus syn-aminopalladation pathways in Pd-catalyzed alkene carboamination reactions of N-allylsulfamides.催化剂结构和反应条件对钯催化的N-烯丙基磺酰胺烯烃碳胺化反应中反式与顺式氨基钯化途径的影响。
Chemistry. 2014 Jul 7;20(28):8782-90. doi: 10.1002/chem.201402258. Epub 2014 Jun 17.
8
Palladium-catalyzed synthesis of 2,1'-disubstituted tetrahydrofurans from gamma-hydroxy internal alkenes. Evidence for alkene insertion into a Pd-O bond and stereochemical scrambling via beta-hydride elimination.钯催化由γ-羟基内烯烃合成2,1'-二取代四氢呋喃。烯烃插入钯-氧键及通过β-氢消除实现立体化学混乱的证据。
J Am Chem Soc. 2005 Nov 30;127(47):16468-76. doi: 10.1021/ja054754v.
9
Asymmetric Palladium-Catalyzed Alkene Carboamination Reactions for the Synthesis of Cyclic Sulfamides.用于合成环状磺酰胺的不对称钯催化烯烃碳胺化反应
Chemistry. 2016 Apr 18;22(17):5919-22. doi: 10.1002/chem.201600887. Epub 2016 Mar 10.
10
Palladium-Catalyzed Aerobic Intramolecular Aminoacetoxylation of Alkenes Enabled by Catalytic Nitrate.钯催化的有氧分子内烯烃的氨甲酰化反应，通过催化硝酸实现。
Org Lett. 2016 Nov 4;18(21):5449-5451. doi: 10.1021/acs.orglett.6b02722. Epub 2016 Oct 18.
引用本文的文献
1
Pd(II)-Catalyzed Aminoacetoxylation of Alkenes Via Tether Formation.钯（II）催化的通过形成连接基实现烯烃的氨基乙酰氧基化反应
Org Lett. 2022 Jul 22;24(28):5068-5072. doi: 10.1021/acs.orglett.2c01838. Epub 2022 Jul 11.
2
Palladium-Catalyzed Organic Reactions Involving Hypervalent Iodine Reagents.钯催化的涉及高价碘试剂的有机反应。
Molecules. 2022 Jun 17;27(12):3900. doi: 10.3390/molecules27123900.
3
Hypervalent Iodine Reagents in Palladium-Catalyzed Oxidative Cross-Coupling Reactions.钯催化氧化交叉偶联反应中的高价碘试剂
Front Chem. 2020 Sep 29;8:705. doi: 10.3389/fchem.2020.00705. eCollection 2020.
4
Directed, Palladium(II)-Catalyzed Intermolecular Aminohydroxylation of Alkenes Using a Mild Oxidation System.导向的、钯(II)催化的烯烃分子间氨羟化反应使用温和的氧化体系。
Org Lett. 2018 Jul 6;20(13):3853-3857. doi: 10.1021/acs.orglett.8b01440. Epub 2018 Jun 11.
5
Palladium-catalysed anti-Markovnikov selective oxidative amination.钯催化的反马氏选择性氧化氨化反应。
Nat Chem. 2018 Mar;10(3):333-340. doi: 10.1038/nchem.2904. Epub 2018 Jan 1.
6
Synthesis of 2,3-Dihydrobenzofurans via the Palladium Catalyzed Carboalkoxylation of 2-Allylphenols.通过钯催化的2-烯丙基苯酚的碳烷氧基化反应合成2,3-二氢苯并呋喃
Org Chem Front. 2016 Oct 1;3(10):1314-1318. doi: 10.1039/C6QO00215C. Epub 2016 Aug 22.
7
Palladium-Catalyzed Aerobic Intramolecular Aminoacetoxylation of Alkenes Enabled by Catalytic Nitrate.钯催化的有氧分子内烯烃的氨甲酰化反应，通过催化硝酸实现。
Org Lett. 2016 Nov 4;18(21):5449-5451. doi: 10.1021/acs.orglett.6b02722. Epub 2016 Oct 18.
8
Asymmetric Palladium-Catalyzed Alkene Carboamination Reactions for the Synthesis of Cyclic Sulfamides.用于合成环状磺酰胺的不对称钯催化烯烃碳胺化反应
Chemistry. 2016 Apr 18;22(17):5919-22. doi: 10.1002/chem.201600887. Epub 2016 Mar 10.
9
Palladium-Catalyzed Alkene Carboamination Reactions of Electron-Poor Nitrogen Nucleophiles.贫电子氮亲核试剂的钯催化烯烃碳胺化反应
Adv Synth Catal. 2015 Jul 6;357(10):2339-2344. doi: 10.1002/adsc.201500334. Epub 2015 Jul 14.
10
The syn/anti-dichotomy in the palladium-catalyzed addition of nucleophiles to alkenes.钯催化亲核试剂与烯烃加成反应中的顺式/反式二分法。
Chemistry. 2015 Jan 2;21(1):36-56. doi: 10.1002/chem.201404070. Epub 2014 Nov 5.
本文引用的文献
1
Homogeneous Oxidation of Alkanes by Electrophilic Late Transition Metals.亲电型后过渡金属对烷烃的均相氧化
Angew Chem Int Ed Engl. 1998 Sep 4;37(16):2180-2192. doi: 10.1002/(SICI)1521-3773(19980904)37:16<2180::AID-ANIE2180>3.0.CO;2-A.
2
Mechanistic studies of Wacker-type amidocyclization of alkenes catalyzed by (IMes)Pd(TFA)2(H2O): kinetic and stereochemical implications of proton transfer.（IMes）Pd（TFA）2（H2O）催化的 Wacker 型烯烃酰胺环化反应的机理研究：质子转移的动力学和立体化学意义。
J Org Chem. 2013 Mar 1;78(5):2083-90. doi: 10.1021/jo302266t. Epub 2012 Nov 30.
3
Reconciling the stereochemical course of nucleopalladation with the development of enantioselective wacker-type cyclizations.协调核钯化的立体化学过程与对映选择性瓦克型环化反应的发展。
Angew Chem Int Ed Engl. 2012 Nov 12;51(46):11505-9. doi: 10.1002/anie.201206702. Epub 2012 Oct 16.
4
Connecting binuclear Pd(III) and mononuclear Pd(IV) chemistry by Pd-Pd bond cleavage.通过钯-钯键的断裂将双核钯(III)和单核钯(IV)化学连接起来。
J Am Chem Soc. 2012 Jul 25;134(29):12002-9. doi: 10.1021/ja304401u. Epub 2012 Jul 17.
5
Palladium-catalyzed vicinal difunctionalization of internal alkenes: diastereoselective synthesis of diamines.钯催化的内烯烃的邻位双官能化反应：二胺的非对映选择性合成。
Angew Chem Int Ed Engl. 2012 Jul 9;51(28):7031-4. doi: 10.1002/anie.201201719. Epub 2012 May 29.
6
High-valent organometallic copper and palladium in catalysis.高价位的有机金属铜和钯在催化中的应用。
Nature. 2012 Apr 11;484(7393):177-85. doi: 10.1038/nature11008.
7
Palladium-catalyzed intermolecular C(sp3)-H amidation.钯催化的分子间C(sp³)-H酰胺化反应。
Angew Chem Int Ed Engl. 2012 Feb 27;51(9):2225-8. doi: 10.1002/anie.201108351. Epub 2012 Feb 1.
8
Hofmann-type rearrangement of imides by in situ generation of imide-hypervalent iodines(III) from iodoarenes.通过碘代芳烃原位生成酰亚胺高价碘(III)实现酰亚胺的霍夫曼型重排。
Org Lett. 2012 Feb 3;14(3):946-9. doi: 10.1021/ol300028j. Epub 2012 Jan 24.
9
Bimetallic redox synergy in oxidative palladium catalysis.双金属氧化还原协同作用在氧化钯催化中的应用。
Acc Chem Res. 2012 Jun 19;45(6):840-50. doi: 10.1021/ar2001974. Epub 2011 Oct 27.
10
Intermolecular oxidative C-N bond formation under metal-free conditions: control of chemoselectivity between aryl sp2 and benzylic sp3 C-H bond imidation.无金属条件下的分子间氧化 C-N 键形成：芳基 sp2 和苄基 sp3 C-H 键亚胺化的化学选择性控制。
J Am Chem Soc. 2011 Oct 19;133(41):16382-5. doi: 10.1021/ja207296y. Epub 2011 Sep 26.
Zotero 插件