• 文献检索
  • 文档翻译
  • 深度研究
  • 学术资讯
  • Suppr Zotero 插件Zotero 插件
  • 邀请有礼
  • 套餐&价格
  • 历史记录
应用&插件
Suppr Zotero 插件Zotero 插件浏览器插件Mac 客户端Windows 客户端微信小程序
定价
高级版会员购买积分包购买API积分包
服务
文献检索文档翻译深度研究API 文档MCP 服务
关于我们
关于 Suppr公司介绍联系我们用户协议隐私条款
关注我们

Suppr 超能文献

核心技术专利：CN118964589B侵权必究
粤ICP备2023148730 号-1Suppr @ 2026

文献检索

告别复杂PubMed语法，用中文像聊天一样搜索，搜遍4000万医学文献。AI智能推荐，让科研检索更轻松。

立即免费搜索

文件翻译

保留排版，准确专业，支持PDF/Word/PPT等文件格式，支持 12+语言互译。

免费翻译文档

深度研究

AI帮你快速写综述，25分钟生成高质量综述，智能提取关键信息，辅助科研写作。

立即免费体验

α-芳基-α-肼基膦酸酯的对映选择性合成。

Enantioselective synthesis of α-aryl α-hydrazino phosphonates.

作者信息

Alberca Saúl, Romero-Parra Javier, Fernández Israel, Fernández Rosario, Lassaletta José M, Monge David

机构信息

Departamento de Química Orgánica, Facultad de Química, Universidad de Sevilla and Centro de Innovación en Química Avanzada (ORFEO-CINQA) C/ Prof. García González, 1 41012 Sevilla Spain

Departamento de Química Orgánica y Fisicoquímica, Facultad de Ciencias Químicas y Farmacéuticas, Universidad de Chile Olivos 1007 Santiago 8380544 Chile.

出版信息

Chem Sci. 2024 Apr 23;15(20):7725-7731. doi: 10.1039/d4sc00822g. eCollection 2024 May 22.

DOI:10.1039/d4sc00822g
PMID:38784752
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC11110148/
Abstract

Catalysts generated by the combination of pyridine-hydrazone ,-ligands and Pd(TFA) have been applied to the addition of arylboronic acids to formylphosphonate-derived hydrazones, yielding α-aryl α-hydrazino phosphonates in excellent enantioselectivities (96 → 99% ee). Subsequent removal of the benzyloxycarbonyl (Cbz) -protecting group afforded key building blocks en route to appealing artificial peptides, herbicides and antitumoral derivatives. Experimental and computational data support a stereochemical model based on aryl-palladium intermediates in which the phosphono hydrazone coordinates in its -configuration, maximizing the interactions between the substrate and the pyridine-hydrazone ligand.

摘要

由吡啶腙配体与Pd(TFA)组合生成的催化剂已应用于芳基硼酸与甲酰基膦酸酯衍生腙的加成反应，以优异的对映选择性（96→99% ee）生成α-芳基α-肼基膦酸酯。随后去除苄氧羰基（Cbz）保护基团，得到了通往引人注目的人工肽、除草剂和抗肿瘤衍生物的关键构建块。实验和计算数据支持基于芳基钯中间体的立体化学模型，其中膦酰腙以其构型配位，使底物与吡啶腙配体之间的相互作用最大化。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/486c/11110148/de517ad94fbe/d4sc00822g-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/486c/11110148/a78fda68cecf/d4sc00822g-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/486c/11110148/2d155f9ab5c5/d4sc00822g-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/486c/11110148/f21e55f247ec/d4sc00822g-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/486c/11110148/dc6d7c35f908/d4sc00822g-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/486c/11110148/5477e0d37d88/d4sc00822g-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/486c/11110148/74146eb21069/d4sc00822g-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/486c/11110148/de517ad94fbe/d4sc00822g-s3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/486c/11110148/a78fda68cecf/d4sc00822g-f1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/486c/11110148/2d155f9ab5c5/d4sc00822g-s1.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/486c/11110148/f21e55f247ec/d4sc00822g-s2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/486c/11110148/dc6d7c35f908/d4sc00822g-f2.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/486c/11110148/5477e0d37d88/d4sc00822g-f3.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/486c/11110148/74146eb21069/d4sc00822g-f4.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/486c/11110148/de517ad94fbe/d4sc00822g-s3.jpg

相似文献

1
Enantioselective synthesis of α-aryl α-hydrazino phosphonates.α-芳基-α-肼基膦酸酯的对映选择性合成。
Chem Sci. 2024 Apr 23;15(20):7725-7731. doi: 10.1039/d4sc00822g. eCollection 2024 May 22.
2
Catalytic enantioselective synthesis of α-aryl α-hydrazino esters and amides.手性催化剂促进的 α-芳基 α-腙酯和酰胺的对映选择性合成。
Chem Commun (Camb). 2020 May 28;56(43):5823-5826. doi: 10.1039/d0cc02478c. Epub 2020 Apr 24.
3
Pyridine-Hydrazones as N,N'-Ligands in Asymmetric Catalysis: Pd(II)-Catalyzed Addition of Boronic Acids to Cyclic Sulfonylketimines.吡啶腙作为不对称催化中的 N,N'-配体：Pd(II)催化硼酸对环状亚砜亚胺的加成反应。
Org Lett. 2015 Oct 16;17(20):5104-7. doi: 10.1021/acs.orglett.5b02613. Epub 2015 Oct 1.
4
Development of Chiral Bis-hydrazone Ligands for the Enantioselective Cross-Coupling Reactions of Aryldimethylsilanolates.用于芳基二甲基硅醇盐对映选择性交叉偶联反应的手性双腙配体的开发
J Org Chem. 2015 Jan 2;80(1):313-66. doi: 10.1021/jo502388r. Epub 2014 Dec 10.
5
Asymmetric organocatalytic synthesis of quaternary α-hydroxy phosphonates: en route to α-aryl phosphaisoserines.季碳α-羟基膦酸酯的不对称有机催化合成：通往α-芳基膦酰基丝氨酸的途径。
Chem Commun (Camb). 2015 Mar 7;51(19):4077-80. doi: 10.1039/c4cc10390d.
6
Rhodium-catalyzed enantioselective hydrogenation of unsaturated phosphonates by ClickFerrophos ligands.铑催化的不饱和膦酸酯的对映选择性氢化反应 通过 ClickFerrophos 配体。
J Org Chem. 2012 Apr 6;77(7):3318-24. doi: 10.1021/jo300129m. Epub 2012 Mar 26.
7
Enantioselective synthesis of sterically hindered α-allyl-α-aryl oxindoles via palladium-catalysed decarboxylative asymmetric allylic alkylation.通过钯催化的脱羧不对称烯丙基烷基化反应对空间位阻α-烯丙基-α-芳基羟吲哚进行对映选择性合成。
Org Biomol Chem. 2017 Oct 4;15(38):8166-8178. doi: 10.1039/c7ob02161e.
8
Enantioselective alpha-arylation of ketones with aryl triflates catalyzed by difluorphos complexes of palladium and nickel.钯和镍的二氟膦配合物催化酮与芳基三氟甲磺酸酯的对映选择性α-芳基化反应。
J Am Chem Soc. 2008 Jan 9;130(1):195-200. doi: 10.1021/ja074453g. Epub 2007 Dec 13.
9
Phosphine-free hydrazone-Pd complex as the catalyst precursor for a Suzuki-Miyaura reaction under mild aerobic conditions.无膦腙-钯配合物作为温和有氧条件下铃木-宫浦反应的催化剂前体。
J Org Chem. 2005 Mar 18;70(6):2191-4. doi: 10.1021/jo048107i.
10
Palladium-Catalyzed Asymmetric Allylic C-H Functionalization: Mechanism, Stereo- and Regioselectivities, and Synthetic Applications.钯催化的不对称烯丙基 C-H 功能化：反应机理、立体和区域选择性及合成应用。
Acc Chem Res. 2020 Dec 15;53(12):2841-2854. doi: 10.1021/acs.accounts.0c00477. Epub 2020 Oct 2.

引用本文的文献

1
Understanding Small Molecule Activation Promoted by Heavier Benzene 1,4-diides: Interplay Between Diradical Character and Aromaticity.理解重质苯1,4 - 二价阴离子促进的小分子活化：双自由基特性与芳香性之间的相互作用
Chemistry. 2025 Aug 13;31(45):e202501933. doi: 10.1002/chem.202501933. Epub 2025 Jun 23.

本文引用的文献

1
The Last Decade of Optically Active α-Aminophosphonates.光学活性α-氨基膦酸酯的过去十年
Molecules. 2023 Aug 20;28(16):6150. doi: 10.3390/molecules28166150.
2
Synthesis of Novel 1,3,4-Oxadiazole-Derived -Aminophosphonates/-Aminophosphonic Acids and Evaluation of Their In Vitro Antiviral Activity against the Avian Coronavirus Infectious Bronchitis Virus.新型1,3,4-恶二唑衍生的α-氨基膦酸酯/α-氨基膦酸的合成及其对禽冠状病毒传染性支气管炎病毒的体外抗病毒活性评价
Pharmaceutics. 2022 Dec 29;15(1):114. doi: 10.3390/pharmaceutics15010114.
3
Relationship between Structure and Antibacterial Activity of α-Aminophosphonate Derivatives Obtained via Lipase-Catalyzed Kabachnik-Fields Reaction.
通过脂肪酶催化的卡巴契克-菲尔德反应获得的α-氨基膦酸酯衍生物的结构与抗菌活性之间的关系
Materials (Basel). 2022 May 27;15(11):3846. doi: 10.3390/ma15113846.
4
Highly Enantioselective Synthesis of [1,2,4]Triazino[5,4-]isoquinoline Derivatives via (3 + 3) Cycloaddition Reactions of Diazo Compounds and Isoquinolinium Methylides.通过重氮化合物与异喹啉叶立德的(3 + 3)环加成反应高度对映选择性合成[1,2,4]三嗪并[5,4 - ]异喹啉衍生物。
Org Lett. 2022 Jun 3;24(21):3766-3771. doi: 10.1021/acs.orglett.2c01122. Epub 2022 May 23.
5
Consecutive Ribosomal Incorporation of α-Aminoxy/α-Hydrazino Acids with l/d-Configurations into Nascent Peptide Chains.连续核糖体将 α-氨氧基/α-腙基氨基酸的 l/d-构型掺入到新生肽链中。
J Am Chem Soc. 2021 Nov 17;143(45):18844-18848. doi: 10.1021/jacs.1c09270. Epub 2021 Nov 3.
6
Amino Acid Based Antimicrobial Agents - Synthesis and Properties.基于氨基酸的抗菌剂 - 合成与性质。
ChemMedChem. 2021 Dec 6;16(23):3513-3544. doi: 10.1002/cmdc.202100503. Epub 2021 Oct 1.
7
Catalytic enantioselective synthesis of α-aryl α-hydrazino esters and amides.手性催化剂促进的 α-芳基 α-腙酯和酰胺的对映选择性合成。
Chem Commun (Camb). 2020 May 28;56(43):5823-5826. doi: 10.1039/d0cc02478c. Epub 2020 Apr 24.
8
Design, synthesis and biological evaluation of novel α-aminophosphonate oxadiazoles via optimized iron triflate catalyzed reaction as apoptotic inducers.新型 α-氨基膦酸恶二唑的设计、合成及铁三氟甲磺酸催化反应的生物评价作为凋亡诱导剂。
Eur J Med Chem. 2019 Oct 15;180:310-320. doi: 10.1016/j.ejmech.2019.07.029. Epub 2019 Jul 11.
9
Recent developments in the synthesis and applications of phosphinic peptide analogs.膦酸肽类似物的合成及应用的最新进展。
Bioorg Med Chem Lett. 2019 May 1;29(9):1031-1042. doi: 10.1016/j.bmcl.2019.02.034. Epub 2019 Feb 28.
10
New 2-Oxoindolin Phosphonates as Novel Agents to Treat Cancer: A Green Synthesis and Molecular Modeling.新型 2-氧代吲哚啉膦酸酯类化合物作为癌症治疗的新型药物：绿色合成与分子模拟。
Molecules. 2018 Aug 8;23(8):1981. doi: 10.3390/molecules23081981.