Manganese‐Catalyzed <i>ortho‐</i>Alkenylation of Aromatic Amidines with Alkynes via C−H Activation

Jia, Teng; Wang, Congyang

doi:10.1002/cctc.201900387

Cited by 20 publications

(12 citation statements)

References 109 publications

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“…We started explorations on manganese organometallic catalysis to address the above challenges from 2013. [13][14][15][16][17][18][19][20][21][22] Accordingly, we have developed a general strategy for manganese organometallic catalysis by leveraging the synergy of manganese catalysts, bases and/or acids. A diverse range of reactivity and reaction categories have been realized through this strategy.…”

Section: Corresponding Authormentioning

confidence: 99%

Manganese-Catalyzed C(sp2)–H Addition to Polar Unsaturated Bonds

Liu

Wang

2021

Synlett

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Transition-metal-catalyzed nucleophilic C-H addition of hydrocarbons to polar unsaturated bonds could intrinsically avoid pre-functionalization of substrates and formation of waste byproducts, thus featuring high step- and atom-economy. As the third most abundant transition metals, manganese-catalyzed C-H addition to polar unsaturated bonds remains challenging partially due to the difficulty in building a closed catalytic cycle of manganese. In the past few years, we have developed manganese catalysis to enable the sp2-hydrid C-H addition to polar unsaturated bonds (e.g. imines, aldehydes, nitriles), which will be mainly discussed in this personal account.

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Section: Corresponding Authormentioning

confidence: 99%

Manganese-Catalyzed C(sp2)–H Addition to Polar Unsaturated Bonds

Liu

Wang

2021

Synlett

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“…In 2013, the Wang group first described the alkenylation of (hetero)arene C−H bonds with terminal alkynes using Mn(CO) 5 Br as the catalyst [5a] . Thereafter, terminal alkynes have been intensively explored in Mn‐catalyzed (hetero)arene C−H bond alkenylation by the groups of Lei and Li, [5b] Wang, [5c,g] Ackermann, [5d] and others, [5e,f,h–j] and Mn(CO) 5 Br catalyst in combination with a base or acid additive or both worked well for these transformations. In contrast, less success has been achieved with the more challenging internal alkynes, and only a handful of procedures are available [6]…”

Section: Introductionmentioning

confidence: 99%

Manganese(I)‐Catalyzed Site‐Selective C6‐Alkenylation of 2‐Pyridones Using Alkynes via C−H Activation

Wan

Luo

et al. 2021

Adv Synth Catal

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A Mn(I)-catalyzed chelation-assisted direct C6À H alkenylation of 2-pyridones with both terminal and internal alkynes in a highly regio-and stereo-selective manner has been developed. The catalytic system consisting of Mn(CO) 5 Br catalyst and KOAc additive allows 1-(2-pyridyl)-2-pyridones to undergo alkenylation with various terminal alkynes in methyl tert-butyl ether (MTBE) to furnish the C6-alkenylated 2-pyridone products in high yields, and the alkenylation with internal alkynes occurs in CH 2 Cl 2 at increased catalyst and additive loadings. Mechanistic studies suggest the involvement of a five-membered organomanganese as the key intermediate in the catalytic cycle.

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“…Amidine has been used as a flexible reaction partner for direct CÀ H activation reaction with alkynes, [14] which include: 1) the C=N-aided monoannulation of amidines with alkynes to easily fabricate isoquinoline, 2) the incorporation of two alkyne units into specific substrates to generate indole-functionalized isoquinoline [15] and 1H-benzo[de] [1,8]naphthyridine derivate, [16] 3) the fourfold CÀ H activation of amidines with alkynes, leading to π-conjugated polycyclic heteroaryl scaffolds, 4) orthoalkenylation of aromatic amidines with alkynes, [17] and others. However, the twofold annulation of amidines with alkynes to furnish benzimidazoisoquinolines has generally remained undeveloped.…”

Section: Introductionmentioning

confidence: 99%

Rhodium(III)‐Catalyzed Oxidative Annulation of Amidines with Alkynes via Sequential C−H Bond Activation

et al. 2021

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In this paper, a rhodium-catalyzed sequential twofold ortho-CÀ H functionalization of N-phenylbenzimidamide with internal alkyne is reported. The double CÀ H activations proved viable in a one-pot fashion with the assistance of C=N and CÀ N bonds, providing a series of benzimidazoisoquinolines with high levels of positional selectivity control. The operationally simple transformation showed high functional group compatibility and featured the cleavage of CÀ H bonds located on different a moiety of the N-phenylbenzimidamide substrates. Detailed mechanistic studies provided strong support for CÀ H bond cleavage on the N-phenyl ring to be preferential compared with CÀ H bond cleavage on C-phenyl ring. As a multifunctional catalytic platform, the rhodium catalyst conducted two independent and compatible catalytic cycles in one pot.

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Manganese‐Catalyzed ortho‐Alkenylation of Aromatic Amidines with Alkynes via C−H Activation

Cited by 20 publications

References 109 publications

Manganese-Catalyzed C(sp2)–H Addition to Polar Unsaturated Bonds

Manganese-Catalyzed C(sp2)–H Addition to Polar Unsaturated Bonds

Manganese(I)‐Catalyzed Site‐Selective C6‐Alkenylation of 2‐Pyridones Using Alkynes via C−H Activation

Rhodium(III)‐Catalyzed Oxidative Annulation of Amidines with Alkynes via Sequential C−H Bond Activation

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