<scp>C</scp>
            –
            <scp>H</scp>
            Functionalization of Arenes Under Palladium/Norbornene Catalysis

Ye, Juntao; Lautens, Mark

doi:10.1002/9783527824137.ch3

“…Interestingly, in the absence of the nucleophile, 1,2‐di‐amination product 8 was isolated in 12 % yield under the standard condition (Scheme 3b). This is a surprising result because intermolecular ipso amination has not been successful by directly using amines as the nucleophile [10d,28] . In addition, our further control experiments show that the Pd‐catalyzed ipso amination cannot take place with the free amine under the standard condition (in the absence of nucleophile and NBE) [29] .…”

Section: Figurementioning

confidence: 99%

Beyond Tertiary Amines: Introducing Secondary Amines by Palladium/Norbornene‐Catalyzed Ortho Amination

Liu,

Zhu,

Dong

2024

Angewandte Chemie

0

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Since the discovery of the palladium/norbornene (Pd/NBE)‐catalyzed ortho amination in 2013, escaping the limitation of only yielding tertiary anilines has been a long‐standing challenge in the past decade. Here, we describe that, by carefully choosing the phosphine ligand and NBE mediator, installation of a N‐mono‐alkylamino group becomes feasible. The reaction tolerates a wide range of aryl iodide substrates and various N‐mono‐tertiary alkylamine‐derived electrophiles. Both ipso alkenylation and alkynylation can be realized. The synthetic utility of this method is exemplified in the formation of primary amino group via selective deprotection and streamlined access to N‐heterocycles. Preliminary success of installing a bulky N‐secondary alkylamino group and mechanistic understanding of the decomposition pathways of mono N‐alkylamine electrophiles have been obtained.

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“…Such a sequence would enable the formation of one C(sp 2 )–O bond and one C(sp 2 )–C(sp 2 ) bond and reconstruction of the benzo-γ-pyrone moiety in a single operation to give difunctionalized chromones, thus representing a significant reaction mode in the vicinal difunctionalization of chromones. Moreover, this protocol represents a complementary approach to the impressive Catellani reaction, which represents another typical method for vicinal difunctionalization of haloarenes …”

mentioning

confidence: 99%

Toward the Generation of 2-Amino-3-Formyl Difunctionalized Chromones via Pd-Enabled Rearrangement Strategy

Tong,

Xiu,

Chen

et al. 2023

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Accomplished herein is a rearrangement strategy for the highly efficient assembly of synthetically cumbersome while medicinally significant 2-amino-3-formyl chromones via palladium-catalyzed ring-opening, rearrangement, and cyclization process. Such a sequence enables the formation of one C(sp2)–O bond and one C(sp2)–C(sp2) bond, and reconstruction of the benzo-γ-pyrone moiety in a single operation, thus producing the difunctionalized chromone-incorporated derivatives. The reaction proceeds in a shorter reaction time (30 min for 3-iodochromones in most cases) in a highly atom- and step-economical manner. The synthetic application of the current protocol is further demonstrated by late-stage modification of pharmaceuticals and their intermediates, gram-scale reactions, transformations of functional groups, as well as the synthesis of bioactive molecules and drugs. Mechanistic studies indicate that a nucleophilic ring-opening process of the benzo-γ-pyrone moiety, phenoxy anion intermediate, and an intramolecular palladium-catalyzed cyclization process might be involved in the present reaction system.

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Beyond Tertiary Amines: Introducing Secondary Amines by Palladium/Norbornene‐Catalyzed Ortho Amination

Liu,

Zhu,

Dong

2024

Angew Chem Int Ed

2

0

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Since the discovery of the palladium/norbornene (Pd/NBE)‐catalyzed ortho amination in 2013, escaping the limitation of only yielding tertiary anilines has been a long‐standing challenge in the past decade. Here, we describe that, by carefully choosing the phosphine ligand and NBE mediator, installation of a N‐mono‐alkylamino group becomes feasible. The reaction tolerates a wide range of aryl iodide substrates and various N‐mono‐tertiary alkylamine‐derived electrophiles. Both ipso alkenylation and alkynylation can be realized. The synthetic utility of this method is exemplified in the formation of primary amino group via selective deprotection and streamlined access to N‐heterocycles. Preliminary success of installing a bulky N‐secondary alkylamino group and mechanistic understanding of the decomposition pathways of mono N‐alkylamine electrophiles have been obtained.

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C – H Functionalization of Arenes Under Palladium/Norbornene Catalysis

Cited by 3 publications

References 153 publications

Beyond Tertiary Amines: Introducing Secondary Amines by Palladium/Norbornene‐Catalyzed Ortho Amination

Beyond Tertiary Amines: Introducing Secondary Amines by Palladium/Norbornene‐Catalyzed Ortho Amination

Toward the Generation of 2-Amino-3-Formyl Difunctionalized Chromones via Pd-Enabled Rearrangement Strategy

Beyond Tertiary Amines: Introducing Secondary Amines by Palladium/Norbornene‐Catalyzed Ortho Amination

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