区域和对映选择性 CuH 催化酮与末端烯丙基的加成反应。
A Regio- and Enantioselective CuH-Catalyzed Ketone Allylation with Terminal Allenes.
机构信息
Department of Chemistry, Massachusetts Institute of Technology , Cambridge, Massachusetts 02139, United States.
出版信息
J Am Chem Soc. 2018 Feb 14;140(6):2007-2011. doi: 10.1021/jacs.7b12271. Epub 2018 Feb 2.
Abstract
We report a method for the highly enantioselective CuH-catalyzed allylation of ketones that employs terminal allenes as allylmetal surrogates. Ketones and allenes bearing diverse and sensitive functional groups are efficiently coupled with high stereoselectivity and exclusive branched regioselectivity. In stoichiometric experiments, each elementary step of the proposed hydrocupration-addition-metathesis mechanism can be followed by NMR spectroscopy.
摘要
我们报告了一种使用末端丙二烯作为烯丙基金属替代物的高度对映选择性 CuH 催化酮的烯丙基化的方法。带有各种敏感官能团的酮和丙二烯可以高效偶联，具有高立体选择性和专一地支化区域选择性。在计量实验中，所提出的水合加成-复分解机理的每个基本步骤都可以通过 NMR 光谱进行跟踪。
相似文献
1
A Regio- and Enantioselective CuH-Catalyzed Ketone Allylation with Terminal Allenes.区域和对映选择性 CuH 催化酮与末端烯丙基的加成反应。
J Am Chem Soc. 2018 Feb 14;140(6):2007-2011. doi: 10.1021/jacs.7b12271. Epub 2018 Feb 2.
2
Regiodivergent and Diastereoselective CuH-Catalyzed Allylation of Imines with Terminal Allenes.区域发散和对映选择性的 CuH 催化亚胺与末端烯丙基的加成反应。
Angew Chem Int Ed Engl. 2016 Nov 2;55(45):14077-14080. doi: 10.1002/anie.201608446. Epub 2016 Oct 10.
3
CuH-Catalyzed Enantioselective Ketone Allylation with 1,3-Dienes: Scope, Mechanism, and Applications.CuH 催化的酮与 1,3-二烯的对映选择性烯丙基化反应：范围、机理和应用。
J Am Chem Soc. 2019 Mar 27;141(12):5062-5070. doi: 10.1021/jacs.9b01784. Epub 2019 Mar 12.
4
Enantioselective and Regiodivergent Addition of Purines to Terminal Allenes: Synthesis of Abacavir.对映选择性和区域选择性嘌呤与末端烯丙基的加成：阿巴卡韦的合成。
Angew Chem Int Ed Engl. 2017 Feb 1;56(6):1520-1524. doi: 10.1002/anie.201610876. Epub 2017 Jan 12.
5
Combining NHC-Cu and Brønsted base catalysis: enantioselective allylic substitution/conjugate additions with alkynylaluminum reagents and stereospecific isomerization of the products to trisubstituted allenes.结合 NHC-Cu 和 Brønsted 碱催化：手性烯丙基取代/共轭加成与炔基铝试剂和产物的立体特异性异构化为三取代丙二烯。
Angew Chem Int Ed Engl. 2013 Jul 22;52(30):7694-9. doi: 10.1002/anie.201303501. Epub 2013 Jun 18.
6
Enantioselective ruthenium-catalyzed carbonyl allylation via alkyne-alcohol C-C bond-forming transfer hydrogenation: allene hydrometalation vs oxidative coupling.通过炔醇碳-碳键形成转移氢化实现对映选择性钌催化的羰基烯丙基化反应：丙二烯氢金属化与氧化偶联
J Am Chem Soc. 2015 Mar 11;137(9):3161-4. doi: 10.1021/jacs.5b00747. Epub 2015 Mar 3.
7
Rhodium-catalyzed chemo-, regio-, and enantioselective addition of 2-pyridones to terminal allenes.铑催化的 2-吡啶酮与末端丙二烯的化学选择性、区域选择性和对映选择性加成。
Angew Chem Int Ed Engl. 2014 Dec 8;53(50):13780-4. doi: 10.1002/anie.201407935. Epub 2014 Oct 8.
8
Sequential Pd-catalyzed asymmetric allene diboration/alpha-aminoallylation.连续钯催化的不对称丙二烯双硼化/α-氨基烯丙基化反应
J Am Chem Soc. 2006 Jan 11;128(1):74-5. doi: 10.1021/ja057020r.
9
Rhodium-Catalyzed Asymmetric N-H Functionalization of Quinazolinones with Allenes and Allylic Carbonates: The First Enantioselective Formal Total Synthesis of (-)-Chaetominine.铑催化喹唑啉酮与丙二烯及烯丙基碳酸酯的不对称N-H官能化反应：（-）-Chaetominine的首次对映选择性形式全合成
Chemistry. 2017 Dec 22;23(72):18156-18160. doi: 10.1002/chem.201705059. Epub 2017 Dec 5.
10
Asymmetric Ni-catalyzed conjugate allylation of activated enones.不对称镍催化的活性烯酮共轭烯丙基化反应。
J Am Chem Soc. 2008 Apr 9;130(14):4978-83. doi: 10.1021/ja710922h. Epub 2008 Mar 14.
引用本文的文献
1
Copper-Catalyzed Diastereo-, Enantio-, and ()-Selective Aminoallylation of Ketones through Reductive Couplings of Azatrienes for the Synthesis of Allylic 1,2-Amino Tertiary Alcohols.通过氮杂三烯的还原偶联实现铜催化的酮的非对映、对映和（）选择性氨基烯丙基化反应以合成烯丙基1,2-氨基叔醇。
J Am Chem Soc. 2024 Jul 24;146(29):20270-20278. doi: 10.1021/jacs.4c05637. Epub 2024 Jul 16.
2
A catalytic process enables efficient and programmable access to precisely altered indole alkaloid scaffolds.一种催化过程能够实现高效、可编程地获得精确修饰的吲哚生物碱支架。
Nat Chem. 2024 Jun;16(6):1003-1014. doi: 10.1038/s41557-024-01455-7. Epub 2024 Feb 19.
3
Chiral α-Stereogenic Oxetanols and Azetidinols Alcohol-Mediated Reductive Coupling of Allylic Acetates: Enantiotopic π-Facial Selection in Symmetric Ketone Addition.手性α-立体异构氧杂环丁醇和氮杂环丁醇 烯丙基乙酸酯的醇介导还原偶联：对称酮加成中的对映异位π-面选择
ACS Catal. 2022 May 20;12(10):6172-6179. doi: 10.1021/acscatal.2c01647. Epub 2022 May 9.
4
Boron-Catalyzed, Diastereo- and Enantioselective Allylation of Ketones with Allenes.硼催化的酮与丙二烯的非对映和对映选择性烯丙基化反应
ACS Catal. 2022 Sep 2;12(17):10887-10893. doi: 10.1021/acscatal.2c03158. Epub 2022 Aug 22.
5
Copper Hydride-Catalyzed Enantioselective Olefin Hydromethylation.铜氢化物催化的对映选择性烯烃氢甲酰化反应。
J Am Chem Soc. 2022 Sep 14;144(36):16303-16309. doi: 10.1021/jacs.2c07489. Epub 2022 Aug 31.
6
Confronting the Challenging Asymmetric Carbonyl 1,2-Addition Using Vinyl Heteroarene Pronucleophiles: Ligand-Controlled Regiodivergent Processes through a Dearomatized Allyl-Cu Species.利用乙烯基杂芳烃给体亲核试剂应对具有挑战性的不对称羰基 1,2-加成：通过去芳构化烯丙基-Cu 物种实现配体控制的区域选择性过程。
J Am Chem Soc. 2022 Apr 6;144(13):5985-5995. doi: 10.1021/jacs.2c00734. Epub 2022 Mar 26.
7
Enantioselective Iridium-Catalyzed Reductive Coupling of Dienes with Oxetanones and N-Acyl-Azetidinones Mediated by 2-Propanol.手性铱催化二烯与环氧酮和 N-酰基氮杂环丁酮的对映选择性还原偶联反应，由 2-丙醇介导。
Angew Chem Int Ed Engl. 2022 Mar 28;61(14):e202115959. doi: 10.1002/anie.202115959. Epub 2022 Feb 16.
8
Synthesis of 1,2-Aminoalcohols through Enantioselective Aminoallylation of Ketones by Cu-Catalyzed Reductive Coupling.酮的铜催化还原偶联对映选择性氨基烯丙基化合成 1,2-氨基醇。
Org Lett. 2021 Aug 20;23(16):6444-6449. doi: 10.1021/acs.orglett.1c02258. Epub 2021 Aug 4.
9
Allenes and Dienes as Chiral Allylmetal Pronucleophiles in Catalytic Enantioselective C=X Addition: Historical Perspective and State-of-The-Art Survey.烯丙基试剂和二烯作为手性烯丙基金属亲核试剂在催化对映选择性 C=X 加成反应中的应用：历史透视和最新进展综述。
Chemistry. 2021 Sep 15;27(52):13107-13116. doi: 10.1002/chem.202101890. Epub 2021 Jul 29.
10
Access to enantioenriched compounds bearing challenging tetrasubstituted stereocenters via kinetic resolution of auxiliary adjacent alcohols.通过辅助邻位醇的动力学拆分获得带有具有挑战性的四取代立体中心的对映体富集化合物。
Nat Commun. 2021 Jun 18;12(1):3735. doi: 10.1038/s41467-021-23990-4.
本文引用的文献
1
Catalytic Hydroalkylation of Allenes.烯丙基的催化氢烷基化反应。
Angew Chem Int Ed Engl. 2017 Dec 4;56(49):15703-15707. doi: 10.1002/anie.201709144. Epub 2017 Nov 13.
2
Enantioselective copper catalysed, direct functionalisation of allenes allyl copper intermediates.对映选择性铜催化的丙二烯直接官能化反应——烯丙基铜中间体
Chem Sci. 2017 Aug 1;8(8):5240-5247. doi: 10.1039/c7sc01968h. Epub 2017 Jun 8.
3
Enantioselective Formation of CF-Bearing All-Carbon Quaternary Stereocenters via C-H Functionalization of Methanol: Iridium Catalyzed Allene Hydrohydroxymethylation.通过甲醇 C-H 功能化构建含 CF 手性全碳季碳中心：铱催化丙二烯的氢羟甲基化反应。
J Am Chem Soc. 2017 Jun 21;139(24):8114-8117. doi: 10.1021/jacs.7b04374. Epub 2017 Jun 12.
4
Enantioselective CuH-Catalyzed Hydroacylation Employing Unsaturated Carboxylic Acids as Aldehyde Surrogates.手性铜氢催化的利用不饱和羧酸作为醛替代物的对映选择性氢酰化反应。
J Am Chem Soc. 2017 Jun 21;139(24):8126-8129. doi: 10.1021/jacs.7b04937. Epub 2017 Jun 6.
5
A Dual Palladium and Copper Hydride Catalyzed Approach for Alkyl-Aryl Cross-Coupling of Aryl Halides and Olefins.钯铜双氢化物催化卤代芳烃与烯烃的烷基芳基交叉偶联反应。
Angew Chem Int Ed Engl. 2017 Jun 12;56(25):7242-7246. doi: 10.1002/anie.201703400. Epub 2017 May 16.
6
Asymmetric Copper Hydride-Catalyzed Markovnikov Hydrosilylation of Vinylarenes and Vinyl Heterocycles.不对称铜氢化物催化的乙烯基芳烃和乙烯基杂环的 Markovnikov 硅氢化反应。
J Am Chem Soc. 2017 Feb 15;139(6):2192-2195. doi: 10.1021/jacs.6b13029. Epub 2017 Feb 1.
7
Metal-catalyzed reductive coupling of olefin-derived nucleophiles: Reinventing carbonyl addition.金属催化的烯烃衍生亲核试剂的还原偶联：羰基加成反应的革新
Science. 2016 Oct 21;354(6310). doi: 10.1126/science.aah5133.
8
Regiodivergent and Diastereoselective CuH-Catalyzed Allylation of Imines with Terminal Allenes.区域发散和对映选择性的 CuH 催化亚胺与末端烯丙基的加成反应。
Angew Chem Int Ed Engl. 2016 Nov 2;55(45):14077-14080. doi: 10.1002/anie.201608446. Epub 2016 Oct 10.
9
Enantioselective Generation of Adjacent Stereocenters in a Copper-Catalyzed Three-Component Coupling of Imines, Allenes, and Diboranes.铜催化的亚胺、丙二烯和二硼烷的三组分偶联反应中立体中心的对映选择性生成。
Angew Chem Int Ed Engl. 2016 Sep 19;55(39):11912-6. doi: 10.1002/anie.201606710. Epub 2016 Aug 19.
10
Balancing C=C Functionalization and C=O Reduction in Cu-H Catalysis.铜-H 催化中 C=C 官能化和 C=O 还原的平衡。
Angew Chem Int Ed Engl. 2016 Sep 26;55(40):12148-9. doi: 10.1002/anie.201606701. Epub 2016 Aug 4.
Zotero 插件