• 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

钯催化的β-氢烷氧基化反应：芳基碘添加剂促进C-H键形成的反常应用。

Palladium-Catalyzed -Hydroalkoxylation: Counterintuitive Use of an Aryl Iodide Additive to Promote C-H Bond Formation.

作者信息

Das Ashis, Buzzetti Luca, Puriņš Mikus, Waser Jerome

机构信息

Laboratory of Catalysis and Organic Synthesis and NCCR Catalysis, Institute of Chemical Sciences and Engineering, Ecole Polytechnique Fédérale de Lausanne, EPFL SB ISIC LCSO, BCH 1402, 1015 Lausanne, Switzerland.

出版信息

ACS Catal. 2022 Jul 1;12(13):7565-7570. doi: 10.1021/acscatal.2c01809. Epub 2022 Jun 13.

DOI:10.1021/acscatal.2c01809
PMID:35799768
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC9251722/
Abstract

We report an enantioselective palladium-catalyzed -hydroalkoxylation of propargylic amines with a trifluoroacetaldehyde-derived tether to build chiral oxazolidines. Diastereoselective hydrogenation using a heterogeneous palladium catalyst then gave access to protected benzylic amino alcohols in 45-87% yields and 84-94% ee values. Hydroalkoxylation of the alkynes required a catalytic amount of aryl iodide, highlighting the counterintuitive key role played by a putative Pd(II)/ArI oxidative addition complex to promote oxypalladation/protodemetalation.

摘要

我们报道了一种对映选择性钯催化的炔丙基胺与三氟乙醛衍生的连接基团的β-氢烷氧基化反应，用于构建手性恶唑烷。然后使用多相钯催化剂进行非对映选择性氢化反应，得到了产率为45-87%、对映体过量值为84-94%的受保护苄基氨基醇。炔烃的氢烷氧基化反应需要催化量的芳基碘化物，这突出了假定的Pd(II)/ArI氧化加成络合物在促进氧钯化/质子脱金属化过程中所起的反直觉关键作用。

https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d8a5/9251722/2fbefcea6112/cs2c01809_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d8a5/9251722/1e7f054fabde/cs2c01809_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d8a5/9251722/0188469273f2/cs2c01809_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d8a5/9251722/aa52f3944d79/cs2c01809_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d8a5/9251722/deccc791a75b/cs2c01809_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d8a5/9251722/2fbefcea6112/cs2c01809_0005.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d8a5/9251722/1e7f054fabde/cs2c01809_0001.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d8a5/9251722/0188469273f2/cs2c01809_0002.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d8a5/9251722/aa52f3944d79/cs2c01809_0003.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d8a5/9251722/deccc791a75b/cs2c01809_0004.jpg
https://cdn.ncbi.nlm.nih.gov/pmc/blobs/d8a5/9251722/2fbefcea6112/cs2c01809_0005.jpg

相似文献

1
Palladium-Catalyzed -Hydroalkoxylation: Counterintuitive Use of an Aryl Iodide Additive to Promote C-H Bond Formation.钯催化的β-氢烷氧基化反应：芳基碘添加剂促进C-H键形成的反常应用。
ACS Catal. 2022 Jul 1;12(13):7565-7570. doi: 10.1021/acscatal.2c01809. Epub 2022 Jun 13.
2
Palladium-Catalyzed Carbo-Oxygenation of Propargylic Amines using in Situ Tether Formation.钯催化炔丙基胺的原位键合碳氧官能团化反应。
Chemistry. 2019 Feb 26;25(12):3010-3013. doi: 10.1002/chem.201900020. Epub 2019 Jan 29.
3
Palladium-catalyzed vicinal amino alcohols synthesis from allyl amines by in situ tether formation and carboetherification.钯催化烯丙基胺原位键合形成和碳醚化合成偕氨基醇。
Angew Chem Int Ed Engl. 2015 Apr 20;54(17):5250-4. doi: 10.1002/anie.201500636. Epub 2015 Feb 26.
4
Palladium(II)-catalyzed highly enantioselective C-H arylation of cyclopropylmethylamines.钯（II）催化的环丙基甲胺的高度对映选择性C-H芳基化反应。
J Am Chem Soc. 2015 Feb 11;137(5):2042-6. doi: 10.1021/ja512529e. Epub 2015 Jan 27.
5
3,3'-Anisyl-substituted BINOL, H(4)BINOL, and H(8)BINOL ligands: asymmetric synthesis of diverse propargylic alcohols and their ring-closing metathesis to chiral cycloalkenes.3,3'-二甲氧基联苯、H(4)BINOL 和 H(8)BINOL 配体：各种丙炔醇的不对称合成及其环化复分解反应生成手性环烯烃。
J Org Chem. 2009 Nov 20;74(22):8681-9. doi: 10.1021/jo9018446.
6
Rare-Earth-Metal-Complex-Catalyzed Hydroalkoxylation and Tandem Hydroalkoxylation/Cyclohydroamination of Isocyanates: Synthesis of Carbamates and Oxazolidinones.稀土金属配合物催化异氰酸酯的氢烷氧基化及串联氢烷氧基化/环氢氨化反应：氨基甲酸酯和恶唑烷酮的合成
Inorg Chem. 2022 Feb 21;61(7):3202-3211. doi: 10.1021/acs.inorgchem.1c03673. Epub 2022 Feb 9.
7
Enantioselective Pd-catalyzed hydrogenation of fluorinated imines: facile access to chiral fluorinated amines.对映选择性 Pd 催化的氟代亚胺氢化反应：手性氟代伯胺的易得途径。
Org Lett. 2010 Nov 5;12(21):5075-7. doi: 10.1021/ol1020256.
8
Enantioselective Carboetherification/Hydrogenation for the Synthesis of Amino Alcohols via a Catalytically Formed Chiral Auxiliary.通过催化形成的手性辅基进行对映选择性碳醚化/氢化反应合成氨基醇。
J Am Chem Soc. 2020 Oct 14;142(41):17334-17339. doi: 10.1021/jacs.0c09177. Epub 2020 Oct 2.
9
Development of palladium-catalyzed transformations using propargylic compounds.使用炔丙基化合物的钯催化转化反应的发展
Chem Pharm Bull (Tokyo). 2012;60(3):285-99. doi: 10.1248/cpb.60.285.
10
Palladium-Catalyzed Arylcarboxylation of Propargylic Alcohols with CO and Aryl Halides: Access to Functionalized α-Alkylidene Cyclic Carbonates.钯催化炔丙醇与 CO 和芳基卤化物的芳基羧化反应：制备功能化的α-烷基烯丙基环碳酸酯。
Org Lett. 2017 Mar 3;19(5):1088-1091. doi: 10.1021/acs.orglett.7b00111. Epub 2017 Feb 23.

本文引用的文献

1
Asymmetric Cyclopropanation and Epoxidation via a Catalytically Formed Chiral Auxiliary.通过催化形成的手性助剂实现不对称环丙烷化和环氧化反应。
Angew Chem Int Ed Engl. 2022 Mar 7;61(11):e202113925. doi: 10.1002/anie.202113925. Epub 2022 Feb 1.
2
Palladium-Catalyzed -Carbosilylation of Alkynes to Access Isoquinolinone-Containing Exocyclic Vinylsilanes.钯催化炔烃的β-碳硅基化反应合成含异喹啉酮的环外乙烯基硅烷
Org Lett. 2021 Aug 6;23(15):5772-5776. doi: 10.1021/acs.orglett.1c01931. Epub 2021 Jul 14.
3
Enantioselective Carboetherification/Hydrogenation for the Synthesis of Amino Alcohols via a Catalytically Formed Chiral Auxiliary.
通过催化形成的手性辅基进行对映选择性碳醚化/氢化反应合成氨基醇。
J Am Chem Soc. 2020 Oct 14;142(41):17334-17339. doi: 10.1021/jacs.0c09177. Epub 2020 Oct 2.
4
Enantioselective radical C-H amination for the synthesis of β-amino alcohols.对映选择性自由基 C-H 胺化反应在β-氨基醇合成中的应用。
Nat Chem. 2020 Aug;12(8):697-704. doi: 10.1038/s41557-020-0482-8. Epub 2020 Jun 22.
5
Stereodivergent Asymmetric Synthesis of α,β-Disubstituted β-Aminoalkylboronic Acid Derivatives via Group-Selective Protodeboronation Enabling Access to the Elusive Anti Isomer.通过选择性原脱硼反应实现α，β-二取代β-氨基烷基硼酸衍生物的立体发散不对称合成，从而获得难以获得的反式异构体。
J Am Chem Soc. 2020 May 13;142(19):9063-9069. doi: 10.1021/jacs.0c03207. Epub 2020 May 4.
6
1,2-Amino Alcohols via Cr/Photoredox Dual-Catalyzed Addition of α-Amino Carbanion Equivalents to Carbonyls.1,2-氨基醇通过 Cr/光氧化还原双重催化α-氨基碳负离子等价物与羰基的加成反应合成。
J Am Chem Soc. 2020 Feb 5;142(5):2168-2174. doi: 10.1021/jacs.9b12053. Epub 2020 Jan 24.
7
Chiral-Organotin-Catalyzed Kinetic Resolution of Vicinal Amino Alcohols.手性有机锡催化的邻氨基醇的动力学拆分
Angew Chem Int Ed Engl. 2019 Nov 4;58(45):16177-16180. doi: 10.1002/anie.201909700. Epub 2019 Sep 30.
8
Regioselective Formal [3+2] Cycloadditions of Urea Substrates with Activated and Unactivated Olefins for Intermolecular Olefin Aminooxygenation.尿素底物与活化和非活化烯烃的区域选择性[3+2]环加成反应用于分子间烯烃氨氧化反应。
Angew Chem Int Ed Engl. 2019 Aug 19;58(34):11676-11680. doi: 10.1002/anie.201904662. Epub 2019 Jul 17.
9
Transition-Metal- and Light-Free Directed Amination of Remote Unactivated C(sp)-H Bonds of Alcohols.过渡金属和光促进的醇类中远程非活化 C(sp3)-H 键的导向氨基化反应。
J Am Chem Soc. 2019 May 22;141(20):8104-8109. doi: 10.1021/jacs.9b04189. Epub 2019 May 8.
10
Palladium-Catalyzed Carbo-Oxygenation of Propargylic Amines using in Situ Tether Formation.钯催化炔丙基胺的原位键合碳氧官能团化反应。
Chemistry. 2019 Feb 26;25(12):3010-3013. doi: 10.1002/chem.201900020. Epub 2019 Jan 29.