Palladium-Catalyzed Regioselective Arylation of Unprotected Allylamines

Overview

Journal JACS Au

Publisher American Chemical Society

Specialty Chemistry

Date 2021 Sep 1

PMID 34467268

Citations 5

Authors

Vinod G Landge

Justin M Maxwell

Pratibha Chand-Thakuri

Mohit Kapoor

Evan T Diemler

Michael C Young

Affiliations

Soon will be listed here.

Abstract

Palladium-catalyzed organometallic transformations of free amines are often unsuccessful due to side reactions, such as oxidation, that can occur. However, the ability to furnish the free amine products from these reactions is important for improving the utility and sustainability of these processes, especially for accessing their potential as medicinal and agrochemical agents. Notably, the 3,3-diarylallylamine motif is prevalent in a variety of biologically relevant structures, yet there are few catalytic approaches to their synthesis, and none involving the free amine. Herein, we describe a simple protocol for the arylation of cinnamylamines and the diarylation of terminal allylamines to generate a diverse group of 3,3-diarylallylamine products using a Pd precatalyst. Key features of the method are the ability to access relatively mild conditions that facilitate a broad substrate scope as well as direct diarylation of terminal allylamine substrates. In addition, several complex and therapeutically relevant molecules are included to demonstrate the utility of the transformation.

Citing Articles

Theoretical study of Ni(0)-catalyzed intermolecular hydroamination of branched 1,3-dienes: reaction mechanism, regioselectivity, enantioselectivity, and prediction of the ligand.

Wang F, Chen C, Zhang F, Meng Q J Mol Model. 2024; 31(1):17.

PMID: 39661131 DOI: 10.1007/s00894-024-06217-3.

Selective C-H Activation of Unprotected Allylamines by Control of Catalyst Speciation.

Landge V, Mishra A, Thotamune W, Bonds A, Alahakoon I, Karunarathne A Chem Catal. 2023; 3(11).

PMID: 37982045 PMC: 10653252. DOI: 10.1016/j.checat.2023.100809.

Transition-Metal-Catalyzed C-H Bond Activation for the Formation of C-C Bonds in Complex Molecules.

Docherty J, Lister T, McArthur G, Findlay M, Domingo-Legarda P, Kenyon J Chem Rev. 2023; 123(12):7692-7760.

PMID: 37163671 PMC: 10311463. DOI: 10.1021/acs.chemrev.2c00888.

Imine Reduction with MeS-BH.

Kamal M, Liu Z, Zhai S, Vidovic D Molecules. 2021; 26(18).

PMID: 34576911 PMC: 8467297. DOI: 10.3390/molecules26185443.

Chiral Hypervalent Iodine Catalysis Enables an Unusual Regiodivergent Intermolecular Olefin Aminooxygenation.

Wu F, Kaur N, Alom N, Li W JACS Au. 2021; 1(6):734-741.

PMID: 34240078 PMC: 8243328. DOI: 10.1021/jacsau.1c00103.

References

Crabtree R . Resolving heterogeneity problems and impurity artifacts in operationally homogeneous transition metal catalysts. Chem Rev. 2011; 112(3):1536-54. DOI: 10.1021/cr2002905. View

Liu Y, Xu H, Kong W, Shang M, Dai H, Yu J . Overcoming the limitations of directed C-H functionalizations of heterocycles. Nature. 2014; 515(7527):389-93. PMC: 4248606. DOI: 10.1038/nature13885. View

Arnold J, Mwenda E, Nguyen H . Rhodium-catalyzed sequential allylic amination and olefin hydroacylation reactions: enantioselective synthesis of seven-membered nitrogen heterocycles. Angew Chem Int Ed Engl. 2014; 53(14):3688-92. DOI: 10.1002/anie.201310354. View

Lai N, Zhu Q, Qiao D, Chen K, Tang L, Wang D . CO Capture With Absorbents of Tertiary Amine Functionalized Nano-SiO. Front Chem. 2020; 8:146. PMC: 7059254. DOI: 10.3389/fchem.2020.00146. View

Hogg K, Trowbridge A, Alvarez-Perez A, Gaunt M . The α-tertiary amine motif drives remarkable selectivity for Pd-catalyzed carbonylation of β-methylene C-H bonds. Chem Sci. 2018; 8(12):8198-8203. PMC: 5855970. DOI: 10.1039/c7sc03876c. View

Derosa J, Kleinmans R, Tran V, Karunananda M, Wisniewski S, Eastgate M . Nickel-Catalyzed 1,2-Diarylation of Simple Alkenyl Amides. J Am Chem Soc. 2018; 140(51):17878-17883. DOI: 10.1021/jacs.8b11942. View

Thornbury R, Saini V, Fernandes T, Santiago C, Talbot E, Sigman M . The development and mechanistic investigation of a palladium-catalyzed 1,3-arylfluorination of chromenes. Chem Sci. 2017; 8(4):2890-2897. PMC: 5376715. DOI: 10.1039/c6sc05102b. View

Furstner A, Ackermann L, Beck K, Hori H, Koch D, Langemann K . Olefin metathesis in supercritical carbon dioxide. J Am Chem Soc. 2001; 123(37):9000-6. DOI: 10.1021/ja010952k. View

Rodrigalvarez J, Nappi M, Azuma H, Floden N, Burns M, Gaunt M . Catalytic C(sp)-H bond activation in tertiary alkylamines. Nat Chem. 2019; 12(1):76-81. DOI: 10.1038/s41557-019-0393-8. View

10.

Ma R, White M . C-H to C-N Cross-Coupling of Sulfonamides with Olefins. J Am Chem Soc. 2018; 140(9):3202-3205. PMC: 6415751. DOI: 10.1021/jacs.7b13492. View

11.

Smalley A, Cuthbertson J, Gaunt M . Palladium-Catalyzed Enantioselective C-H Activation of Aliphatic Amines Using Chiral Anionic BINOL-Phosphoric Acid Ligands. J Am Chem Soc. 2017; 139(4):1412-1415. DOI: 10.1021/jacs.6b12234. View

12.

Tafazolian H, Schmidt J . Cationic [(Iminophosphine)Nickel(Allyl)] Complexes as the First Example of Nickel Catalysts for Direct Hydroamination of Allenes. Chemistry. 2016; 23(7):1507-1511. DOI: 10.1002/chem.201605611. View

13.

Yin Z, Ye J, Zhou W, Zhang Y, Ding L, Gui Y . Oxy-Difluoroalkylation of Allylamines with CO via Visible-Light Photoredox Catalysis. Org Lett. 2017; 20(1):190-193. DOI: 10.1021/acs.orglett.7b03551. View

14.

Trowbridge A, Walton S, Gaunt M . New Strategies for the Transition-Metal Catalyzed Synthesis of Aliphatic Amines. Chem Rev. 2020; 120(5):2613-2692. DOI: 10.1021/acs.chemrev.9b00462. View

15.

Wu Z, Fatuzzo N, Dong G . Distal Alkenyl C-H Functionalization via the Palladium/Norbornene Cooperative Catalysis. J Am Chem Soc. 2020; 142(6):2715-2720. PMC: 7075342. DOI: 10.1021/jacs.9b11479. View

16.

Prediger P, Ferreira Barbosa L, Genisson Y, Roque Duarte Correia C . Substrate-directable Heck reactions with arenediazonium salts. The regio- and stereoselective arylation of allylamine derivatives and applications in the synthesis of naftifine and abamines. J Org Chem. 2011; 76(19):7737-49. DOI: 10.1021/jo201105z. View

17.

Ross S, Rahman A, Sigman M . Development and Mechanistic Interrogation of Interrupted Chain-Walking in the Enantioselective Relay Heck Reaction. J Am Chem Soc. 2020; 142(23):10516-10525. PMC: 7376753. DOI: 10.1021/jacs.0c03589. View

18.

Delcamp J, Brucks A, White M . A general and highly selective chelate-controlled intermolecular oxidative Heck reaction. J Am Chem Soc. 2008; 130(34):11270-1. DOI: 10.1021/ja804120r. View

19.

Bhattacharya T, Pimparkar S, Maiti D . Combining transition metals and transient directing groups for C-H functionalizations. RSC Adv. 2022; 8(35):19456-19464. PMC: 9080754. DOI: 10.1039/c8ra03230k. View

20.

Heel R, Morley P, Brogden R, Carmine A, Speight T, Avery G . Zimelidine: a review of its pharmacological properties and therapeutic efficacy in depressive illness. Drugs. 1982; 24(3):169-206. DOI: 10.2165/00003495-198224030-00001. View