Native amine-directed site-selective C(sp3)-H arylation of primary aliphatic amines with aryl iodides

Pramanick, Pranab K.; Zhou, Zhibing; Hou, Zhen-Lin; Ao, Yu‐Fei; Yao, Bo

doi:10.1016/j.cclet.2019.10.034

Cited by 13 publications

(6 citation statements)

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“… These researchers significantly improved the scope of γ-methylene-C(sp 3 )–H heteroarylation of free amines and extended to δ-C(sp 3 )–H arylation of aliphatic amines through ligand development . Likewise, Yao and co-workers reported a Pd(OAc) 2 -catalyzed free amine-directed site-selective γ- and δ-C(sp 3 )–H arylation of primary aliphatic amines with aryl iodides in 85:15 HFIP/AcOH . Furthermore, Jiang and Liu used DG A in their Pd-catalyzed direct γ-C(sp3)–H arylation of free β2-amino esters and β3-amino esters, which employed a 10:1 HFIP/AcOH solvent medium …”

Section: C–h Functionalization Reactionsmentioning

confidence: 99%

HFIP in Organic Synthesis

et al. 2022

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1,1,1,3,3,3-Hexafluoroisopropanol (HFIP) is a polar, strongly hydrogen bond-donating solvent that has found numerous uses in organic synthesis due to its ability to stabilize ionic species, transfer protons, and engage in a range of other intermolecular interactions. The use of this solvent has exponentially increased in the past decade and has become a solvent of choice in some areas, such as C–H functionalization chemistry. In this review, following a brief history of HFIP in organic synthesis and an overview of its physical properties, literature examples of organic reactions using HFIP as a solvent or an additive are presented, emphasizing the effect of solvent of each reaction.

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Section: C–h Functionalization Reactionsmentioning

confidence: 99%

HFIP in Organic Synthesis

et al. 2022

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“… 32 , 33 Recent advances have been made with the use of free amines as native directing groups, typically using acidic media to help protect the amine from oxidation. 34 − 37 However, the most common workaround is to convert the amine in situ to a better, transient directing group. 38 − 41 Based on this precedent, our group recently explored the use of CO 2 as a transient directing group and simultaneously transient protecting group for C–H arylation of aliphatic 42 and benzylic substrates.…”

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confidence: 99%

“…One challenge in using free amines as substrates is that amines are typically poor directing groups on their own, − unless steric bulk, substitution, or exogenous ligands are used to inhibit decomposition pathways or formation of unreactive intermediates. , Recent advances have been made with the use of free amines as native directing groups, typically using acidic media to help protect the amine from oxidation. − However, the most common workaround is to convert the amine in situ to a better, transient directing group. − Based on this precedent, our group recently explored the use of CO 2 as a transient directing group and simultaneously transient protecting group for C–H arylation of aliphatic and benzylic substrates . We wondered whether or not a similar approach could be applied to the functionalization of allylamine substrates (Scheme c) without the need for additional protection/deprotection steps.…”

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confidence: 99%

Palladium-Catalyzed Regioselective Arylation of Unprotected Allylamines

Landge

Maxwell

Chand-Thakuri

et al. 2020

JACS Au

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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 II 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.

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“…Using native amino groups, without preinstalled directing groups (DGs) or transient directing groups (TDGs), for the C–H activation reactions would be an ideal strategy. However, only a few examples of free primary amines as native DGs were reported …”

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confidence: 99%

Native Amino Group Directed Site-Selective ε-C(sp²)–H Iodination of Primary Amines

et al. 2023

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Selective remote C–H activating amines using unmodified NH2 as a native directing group demonstrate compelling synthetic utilities. The 3-arylpropan-1-amine moiety is present in many drugs and candidates in clinical trials. Selective iodination of 3-arylpropan-1-amines on remote aryl rings gives valuable intermediates for modifying bioactive molecules and synthesizing quinolones. Here we report the first palladium-catalyzed selective ε-C(sp2)–H iodination of free 3-arylpropan-1-amines via a seven-membered palladacycle.

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Native amine-directed site-selective C(sp3)-H arylation of primary aliphatic amines with aryl iodides

Cited by 13 publications

References 50 publications

HFIP in Organic Synthesis

HFIP in Organic Synthesis

Palladium-Catalyzed Regioselective Arylation of Unprotected Allylamines

Native Amino Group Directed Site-Selective ε-C(sp²)–H Iodination of Primary Amines

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Native amine-directed site-selective C(sp3)-H arylation of primary aliphatic amines with aryl iodides

Cited by 13 publications

References 50 publications

HFIP in Organic Synthesis

HFIP in Organic Synthesis

Palladium-Catalyzed Regioselective Arylation of Unprotected Allylamines

Native Amino Group Directed Site-Selective ε-C(sp2)–H Iodination of Primary Amines

Contact Info

Product

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Native Amino Group Directed Site-Selective ε-C(sp²)–H Iodination of Primary Amines