Easily Accessible Auxiliary for Palladium‐Catalyzed Intramolecular Amination of C(sp<sup>2</sup>)H and C(sp<sup>3</sup>)H Bonds at δ‐ and ε‐Positions

Wang, Chao; Chen, Changpeng; Zhang, Jingyu; Han, Jianlin; Wang, Qian; Guo, Kun; Liu, Pei; Guan, Mingyu; Yao, Yingming; Zhao, Yingsheng

doi:10.1002/ange.201404854

Cited by 38 publications

(7 citation statements)

References 63 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Reductive elimination to forge the C(sp 3 )–N bond is faster than C(sp 3 )–OAc bond formation, thus giving the desired lactam product. 130–132 In a subsequent manuscript, Chen also reported an example of C(sp 3 )–H alkoxylation using the same substrate 122 , in which C(sp 3 )–OR bond-forming reductive elimination to give 131 is more facile than the C(sp 3 )–N bond-forming cyclization when the reaction was carried out in the presence of alcohols. 133 Using cyclic hypervalent iodine as the oxidant, Rao and co-workers further optimized the protocols to cleave β-methyl as well as β-methylene C(sp 3 )–H bonds of aliphatic acid-derived amides, constructing C(sp 3 )–O bonds with broad substrate scopes.…”

Section: C(sp3)–h Activation Directed By Strongly Coordinating Auxmentioning

confidence: 98%

Palladium-Catalyzed Transformations of Alkyl C–H Bonds

et al. 2016

View full text Add to dashboard Cite

This Review summarizes the advancements in Pd-catalyzed C(sp3)–H activation via various redox manifolds, including Pd(0)/Pd(II), Pd(II)/Pd(IV), and Pd(II)/Pd(0). While few examples have been reported in the activation of alkane C–H bonds, many C(sp3)–H activation/C–C and C–heteroatom bond forming reactions have been developed by the use of directing group strategies to control regioselectivity and build structural patterns for synthetic chemistry. A number of mono- and bidentate ligands have also proven to be effective for accelerating C(sp3)–H activation directed by weakly coordinating auxiliaries, which provides great opportunities to control reactivity and selectivity (including enantioselectivity) in Pd-catalyzed C–H functionalization reactions.

show abstract

Section: C(sp3)–h Activation Directed By Strongly Coordinating Auxmentioning

confidence: 98%

Palladium-Catalyzed Transformations of Alkyl C–H Bonds

et al. 2016

View full text Add to dashboard Cite

show abstract

“…Since the pioneering works of Daugulis and Chen (G.) demonstrating that bidentate auxiliaries are effective for oxidative cyclization under Pd(II)/Pd(IV) catalysis, a variety of bidentate directing groups have been examined in indoline synthesis. More specifically, the 1,2,3-triazole-4-carboxylate, 105 2-pyridylsulfonyl, 106 oxalyl amide, 107 and 2-methoxyiminoac-yl 108 directing group have been employed for the oxidative synthesis of indolines under varied conditions (Scheme 17).…”

Section: Directing Group-assisted C−h Activation Catalysismentioning

confidence: 99%

Transition Metal-Catalyzed C–H Amination: Scope, Mechanism, and Applications

2017

View full text Add to dashboard Cite

Catalytic transformation of ubiquitous C-H bonds into valuable C-N bonds offers an efficient synthetic approach to construct N-functionalized molecules. Over the last few decades, transition metal catalysis has been repeatedly proven to be a powerful tool for the direct conversion of cheap hydrocarbons to synthetically versatile amino-containing compounds. This Review comprehensively highlights recent advances in intra- and intermolecular C-H amination reactions utilizing late transition metal-based catalysts. Initial discovery, mechanistic study, and additional applications were categorized on the basis of the mechanistic scaffolds and types of reactions. Reactivity and selectivity of novel systems are discussed in three sections, with each being defined by a proposed working mode.

show abstract

“…In 2014, Yao, Zhao, and co-workers reported intramolecular d-C-H amination of oxalyl amide-protected amines (41) to pyrrolidine derivatives (43) via six-membered palladacycle intermediates (42, Scheme 11B). 50 Using PhI(OAc) 2 , good yields of cyclized products were obtained. Notably, the unbranched n-butylamine derivative (41, R 1 = R 2 = R 3 = H) gave 25% yield of the pyrrolidine product.…”

Section: Pd(ii)/pd(iv) Catalysismentioning

confidence: 99%

Palladium-Catalyzed C(sp3)–H Bond Functionalization of Aliphatic Amines

Whitehurst

Gaunt

2019

Chem

221

119

View full text Add to dashboard Cite

Methods that enable the practical and selective functionalization of traditionally unreactive aliphatic C-H bonds have synthetic applications in fields ranging from drug discovery to advanced materials. One of the major challenges is the development of strategically important reactions on aliphatic molecules containing synthetically useful functional groups. Aliphatic amines are central to the function of many biologically active molecules, as evidenced by their prevalence in a large number of pharmaceutical agents. Over the past decade, chemists have found ways to tailor the electronic and steric properties of directing functionalities and ligands to enable palladium-catalyzed C-H activation of aliphatic amine derivatives. Many of these methods have been successfully applied to the synthesis of pharmaceuticals and complex natural products. This review provides an overview of these methods and describes recent contributions, as well as the remaining challenges, in this emerging field.

show abstract

Easily Accessible Auxiliary for Palladium‐Catalyzed Intramolecular Amination of C(sp²)H and C(sp³)H Bonds at δ‐ and ε‐Positions

Cited by 38 publications

References 63 publications

Palladium-Catalyzed Transformations of Alkyl C–H Bonds

Palladium-Catalyzed Transformations of Alkyl C–H Bonds

Transition Metal-Catalyzed C–H Amination: Scope, Mechanism, and Applications

Palladium-Catalyzed C(sp3)–H Bond Functionalization of Aliphatic Amines

Contact Info

Product

Resources

About

Easily Accessible Auxiliary for Palladium‐Catalyzed Intramolecular Amination of C(sp2)H and C(sp3)H Bonds at δ‐ and ε‐Positions

Cited by 38 publications

References 63 publications

Palladium-Catalyzed Transformations of Alkyl C–H Bonds

Palladium-Catalyzed Transformations of Alkyl C–H Bonds

Transition Metal-Catalyzed C–H Amination: Scope, Mechanism, and Applications

Palladium-Catalyzed C(sp3)–H Bond Functionalization of Aliphatic Amines

Contact Info

Product

Resources

About

Easily Accessible Auxiliary for Palladium‐Catalyzed Intramolecular Amination of C(sp²)H and C(sp³)H Bonds at δ‐ and ε‐Positions