手性 C1 对称 NHC-Cu 配合物催化（频哪醇硼酸酯）烯丙基硼与取代芳基、杂芳基、烷基或烯基取代亚胺的反应对映选择性合成高烯丙基胺。
Enantioselective synthesis of homoallylic amines through reactions of (pinacolato)allylborons with aryl-, heteroaryl-, alkyl-, or alkene-substituted aldimines catalyzed by chiral C1-symmetric NHC-Cu complexes.
机构信息
Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, Massachusetts 02467, United States.
出版信息
J Am Chem Soc. 2011 Mar 16;133(10):3332-5. doi: 10.1021/ja200311n. Epub 2011 Feb 22.
Abstract
A catalytic method for enantioselective synthesis of homoallylamides through Cu-catalyzed reactions of stable and easily accessible (pinacolato)allylborons with aryl-, heteroaryl-, alkyl-, or alkenyl-substituted N-phosphinoylimines is disclosed. Transformations are promoted by 1-5 mol % of readily accessible NHC-Cu complexes, derived from C(1)-symmetric imidazolinium salts, which can be prepared in multigram quantities in four steps from commercially available materials. Allyl additions deliver the desired products in up to quantitative yield and 98.5:1.5 enantiomeric ratio and are amenable to gram-scale operations. A mechanistic model accounting for the observed selectivity levels and trends is proposed.
摘要
一种通过 Cu 催化稳定且易于获得的（频哪醇基）烯丙基硼与取代的芳基、杂芳基、烷基或烯基取代的 N-膦酰亚胺的反应对映选择性合成高烯丙基酰胺的催化方法。转化由易于获得的 NHC-Cu 配合物促进，该配合物由 C(1)-对称咪唑啉盐衍生而来，可从商业上可获得的材料通过四步反应以多克量制备。烯丙基加成以高达定量产率和 98.5:1.5 的对映体比例提供所需产物，并且适用于克级操作。提出了一个能够解释观察到的选择性水平和趋势的机理模型。
相似文献
1
Enantioselective synthesis of homoallylic amines through reactions of (pinacolato)allylborons with aryl-, heteroaryl-, alkyl-, or alkene-substituted aldimines catalyzed by chiral C1-symmetric NHC-Cu complexes.手性 C1 对称 NHC-Cu 配合物催化（频哪醇硼酸酯）烯丙基硼与取代芳基、杂芳基、烷基或烯基取代亚胺的反应对映选择性合成高烯丙基胺。
J Am Chem Soc. 2011 Mar 16;133(10):3332-5. doi: 10.1021/ja200311n. Epub 2011 Feb 22.
2
N-Heterocyclic Carbene-Copper-Catalyzed Group-, Site-, and Enantioselective Allylic Substitution with a Readily Accessible Propargyl(pinacolato)boron Reagent: Utility in Stereoselective Synthesis and Mechanistic Attributes.N-杂环卡宾-铜催化的具有易得丙炔基（频哪醇）硼试剂的基团、位点和对映选择性烯丙基取代反应：在立体选择性合成中的应用和反应机理。
J Am Chem Soc. 2015 Jul 22;137(28):8948-64. doi: 10.1021/jacs.5b05805. Epub 2015 Jul 14.
3
A broadly applicable NHC-Cu-catalyzed approach for efficient, site-, and enantioselective coupling of readily accessible (pinacolato)alkenylboron compounds to allylic phosphates and applications to natural product synthesis.一种广泛适用的 NHC-Cu 催化方法，用于高效、位点和对映选择性地偶联易得的（频哪醇基）烯基硼化合物与烯丙基磷酸酯，并应用于天然产物合成。
J Am Chem Soc. 2014 Feb 5;136(5):2149-61. doi: 10.1021/ja4126565. Epub 2014 Jan 28.
4
Efficient boron-copper additions to aryl-substituted alkenes promoted by NHC-based catalysts. enantioselective Cu-catalyzed hydroboration reactions.NHC 基催化剂促进的芳基取代烯烃的高效硼铜加成反应。对映选择性 Cu 催化的硼氢化反应。
J Am Chem Soc. 2009 Mar 11;131(9):3160-1. doi: 10.1021/ja809382c.
5
Monodentate non-C(2)-symmetric chiral N-heterocyclic carbene complexes for enantioselective synthesis. Cu-catalyzed conjugate additions of aryl- and alkenylsilylfluorides to cyclic enones.用于对映选择性合成的单齿非C(2)对称手性N-杂环卡宾配合物。铜催化芳基和烯基甲硅烷基氟化物对环状烯酮的共轭加成反应。
J Org Chem. 2009 Jun 19;74(12):4455-62. doi: 10.1021/jo900589x.
6
Enantioselective synthesis of boron-substituted quaternary carbons by NHC-Cu-catalyzed boronate conjugate additions to unsaturated carboxylic esters, ketones, or thioesters.手性 NHC-Cu 催化硼酸盐与不饱和羧酸酯、酮或硫酯的共轭加成反应合成硼取代的季碳中心
J Am Chem Soc. 2010 Aug 11;132(31):10630-3. doi: 10.1021/ja104777u.
7
NHC-Cu-catalyzed addition of propargylboron reagents to phosphinoylimines. Enantioselective synthesis of trimethylsilyl-substituted homoallenylamides and application to the synthesis of S-(-)-cyclooroidin.NHC-铜催化炔丙基硼试剂与磷酰亚胺的加成反应。三甲基硅基取代的高烯丙基酰胺的对映选择性合成及其在S-(-)-环奥罗定合成中的应用。
J Am Chem Soc. 2014 Mar 5;136(9):3362-5. doi: 10.1021/ja500373s. Epub 2014 Feb 20.
8
Regio- and Enantioselective Synthesis of Trifluoromethyl-Substituted Homoallylic α-Tertiary NH -Amines by Reactions Facilitated by a Threonine-Based Boron-Containing Catalyst.基于苏氨酸的含硼催化剂促进的区域和对映选择性合成三氟甲基取代的偕丙基α-叔氨-NH-胺的反应。
Angew Chem Int Ed Engl. 2020 Jul 6;59(28):11448-11455. doi: 10.1002/anie.202001184. Epub 2020 May 8.
9
An efficient, practical, and enantioselective method for synthesis of homoallenylamides catalyzed by an aminoalcohol-derived, boron-based catalyst.一种由氨基醇衍生的硼基催化剂催化合成高烯丙基酰胺的高效、实用且对映选择性方法。
J Am Chem Soc. 2014 Mar 12;136(10):3780-3. doi: 10.1021/ja500374p. Epub 2014 Mar 3.
10
Exceptionally E- and β-selective NHC-Cu-catalyzed proto-silyl additions to terminal alkynes and site- and enantioselective proto-boryl additions to the resulting vinylsilanes: synthesis of enantiomerically enriched vicinal and geminal borosilanes.异常的 E- 和 β-选择性 NHC-Cu 催化的末端炔烃的原硅烷基加成以及生成的乙烯基硅烷的位点和对映选择性原硼酸酯加成：对映体富集的偕二硼硅烷和连二硼硅烷的合成。
Chemistry. 2013 Feb 25;19(9):3204-14. doi: 10.1002/chem.201203803. Epub 2013 Jan 16.
引用本文的文献
1
IPr**-Highly Hindered, Ring Extended N-Heterocyclic Carbenes.IPr**-高度受阻、环扩展的氮杂环卡宾。
Organometallics. 2025 Aug 7;44(16):1848-53. doi: 10.1021/acs.organomet.5c00232.
2
Catalytic prenyl conjugate additions for synthesis of enantiomerically enriched PPAPs.催化烯丙基共轭加成反应合成对映体富集的 PPAPs。
Science. 2024 Oct 11;386(6718):167-175. doi: 10.1126/science.adr8612. Epub 2024 Oct 10.
3
Asymmetric Reactions of -Phosphonyl/Phosphoryl Imines.磷酰基/膦酰基亚胺的不对称反应。
Molecules. 2023 Apr 17;28(8):3524. doi: 10.3390/molecules28083524.
4
Copper(I)-catalyzed asymmetric 1,6-conjugate allylation.铜（I）催化的不对称 1,6-共轭烯丙基化反应。
Nat Commun. 2020 Oct 30;11(1):5480. doi: 10.1038/s41467-020-19293-9.
5
Copper-Catalyzed Borylative Couplings with C-N Electrophiles.铜催化的与 C-N 亲电试剂的硼化偶联反应。
Angew Chem Int Ed Engl. 2020 Nov 9;59(46):20278-20289. doi: 10.1002/anie.202007251. Epub 2020 Jul 28.
6
Cu-Catalyzed Diastereo- and Enantioselective Reactions of γ,γ-Disubstituted Allyldiboron Compounds with Ketones.铜催化的γ,γ-二取代烯丙基二硼化合物与酮的非对映选择性和对映选择性反应。
Angew Chem Int Ed Engl. 2020 May 25;59(22):8451-8455. doi: 10.1002/anie.202000675. Epub 2020 Mar 24.
7
Diastereo- and Enantioselective Synthesis of Homoallylic Amines Bearing Quaternary Carbon Centers.具有季碳中心的非对映和对映选择性合成偕丙基胺。
J Am Chem Soc. 2020 Jan 29;142(4):1704-1709. doi: 10.1021/jacs.9b11529. Epub 2020 Jan 17.
8
A Regio- and Stereodivergent Synthesis of Homoallylic Amines by a One-Pot Cooperative-Catalysis-Based Allylic Alkylation/Hofmann Rearrangement Strategy.通过一锅协同催化的烯丙基烷基化/霍夫曼重排策略实现高烯丙基胺的区域和立体选择性合成。
Angew Chem Int Ed Engl. 2019 Jul 29;58(31):10521-10527. doi: 10.1002/anie.201905426. Epub 2019 Jun 28.
9
Synergistic catalysis for cascade allylation and 2-aza-cope rearrangement of azomethine ylides.用于甲亚胺叶立德的串联烯丙基化反应和2-氮杂-Cope重排反应的协同催化作用。
Nat Commun. 2019 Apr 8;10(1):1594. doi: 10.1038/s41467-019-09563-6.
10
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.
本文引用的文献
1
Indium-mediated catalytic enantioselective allylation of N-benzoylhydrazones using a protonated chiral amine.铟介导的质子化手性伯胺催化 N-苯甲酰腙的对映选择性烯丙基化反应。
J Am Chem Soc. 2010 Sep 8;132(35):12168-9. doi: 10.1021/ja1035336.
2
Enantioselective synthesis of allylboronates bearing a tertiary or quaternary B-substituted stereogenic carbon by NHC-Cu-catalyzed substitution reactions.手性 NHC-Cu 催化取代反应合成含叔碳或季碳手性取代基的烯丙基硼酸酯
J Am Chem Soc. 2010 Aug 11;132(31):10634-7. doi: 10.1021/ja104254d.
3
Enantioselective synthesis of boron-substituted quaternary carbons by NHC-Cu-catalyzed boronate conjugate additions to unsaturated carboxylic esters, ketones, or thioesters.手性 NHC-Cu 催化硼酸盐与不饱和羧酸酯、酮或硫酯的共轭加成反应合成硼取代的季碳中心
J Am Chem Soc. 2010 Aug 11;132(31):10630-3. doi: 10.1021/ja104777u.
4
Identification of modular chiral bisphosphines effective for Cu(i)-catalyzed asymmetric allylation and propargylation of ketones.识别对酮的 Cu(i)-催化不对称烯丙基化和炔丙基化有效的模块化手性双膦配体。
J Am Chem Soc. 2010 May 19;132(19):6638-9. doi: 10.1021/ja101948s.
5
Enantioselective conjugate silyl additions to cyclic and acyclic unsaturated carbonyls catalyzed by Cu complexes of chiral N-heterocyclic carbenes.手性氮杂环卡宾铜配合物催化的环状和非环状不饱和羰基化合物的对映选择性共轭硅烷加成反应。
J Am Chem Soc. 2010 Mar 10;132(9):2898-900. doi: 10.1021/ja910989n.
6
Indium(I)-catalyzed asymmetric allylation, crotylation, and alpha-chloroallylation of hydrazones with rare constitutional and high configurational selectivities.铟（I）催化腙的不对称烯丙基化、巴豆基化和α-氯烯丙基化反应，具有罕见的结构选择性和高构型选择性。
Angew Chem Int Ed Engl. 2010 Mar 1;49(10):1838-41. doi: 10.1002/anie.200906308.
7
Asymmetric allylation, crotylation, and cinnamylation of N-heteroaryl hydrazones.N-杂芳基腙的不对称烯丙基化、巴豆基化和肉桂基化。
Org Lett. 2010 Feb 19;12(4):688-91. doi: 10.1021/ol9026864.
8
Enantioselective Ag-Catalyzed Allylation of Aldimines.银催化醛亚胺的对映选择性烯丙基化反应
European J Org Chem. 2009 Aug 26;2009(30):5129-5131. doi: 10.1002/ejoc.200900669.
9
Allylcopper intermediates with N-heterocyclic carbene ligands: synthesis, structure, and catalysis.烯丙基铜与 N-杂环卡宾配体的中间体：合成、结构和催化作用。
Org Lett. 2010 Jan 15;12(2):220-3. doi: 10.1021/ol902458v.
10
Stereogenic-at-metal Zn- and Al-based N-heterocyclic carbene (NHC) complexes as bifunctional catalysts in Cu-free enantioselective allylic alkylations.基于金属锌和铝的具有手性中心的氮杂环卡宾（NHC）配合物作为无铜对映选择性烯丙基烷基化反应中的双功能催化剂。
J Am Chem Soc. 2009 Aug 19;131(32):11625-33. doi: 10.1021/ja904654j.
Zotero 插件