Dual Ligand-Enabled Nondirected C–H Cyanation of Arenes

Chen, Hao; Mondal, Arup; Gemmeren, Manuel van

doi:10.26434/chemrxiv.7182095.v1

Cited by 3 publications

(2 citation statements)

References 7 publications

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“…Very recently ligand approaches have been devised which helped in overcoming the reactivity issue and expanded the scope to various arenes and heteroarenes (Fig. 1b) 3,4 . However, the regioselectivity with most arenes still remains problematic, unless the (hetero)arene is sterically or electronically biased.…”

Section: Main Textmentioning

confidence: 99%

Photoinduced Regioselective Olefination of Arenes at Proximal and Distal Sites

et al. 2022

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The Fujiwara-Moritani reaction has had a profound contribution in the emergence of contemporary C-H activation protocols. Despite the applicability of the traditional approach in different elds, the associated reactivity and regioselectivity issues had rendered it redundant. The revival of this exemplary reaction requires the development of a mechanistic paradigm that would have simultaneous control on both the reactivity and regioselectivity. Often high thermal energy required to promote ole nation leads to multiple site functionalization. To this aim we established a photoredoxcatalytic system constituting a merger of palladium/organo-photocatalyst that forges oxidative ole nation in an explicit regioselective fashion of diverse arenes and heteroarenes. Visible light plays a signi cant role in executing 'regio-resolved' Fuijiwara-Moritani reaction without the requirement of silver salts and thermal energy. The catalytic system is also amenable towards proximal and distal ole nation aided by respective directing groups (DGs), which entails the versatility of the protocol in engaging the entire spectrum of C(sp2)-H ole nation.Furthermore, streamlining the synthesis of natural products, chiral molecules, drugs and diversi cation through late-stage functionalizations underscore the importance of this sustainable protocol. The photoinduced attainment of this regioselective transformation is mechanistically established through control reactions, kinetic studies and theoretical calculations.

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Section: Main Textmentioning

confidence: 99%

Photoinduced Regioselective Olefination of Arenes at Proximal and Distal Sites

et al. 2022

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“…343 Simultaneously van Gemmeren and co-workers reported same transformation, which induced the involvement of N-acetyl−glycine and (3-trifluoromethyl)quinoline as ligand systems. 344 In a contemporary study, Yu's group utilized pyridine based ligand system to perform nondirected C−H cyanation for arene limited system. 345 Toluene could be cyanated to give the respective cyanated product in 80% yield and possessing an ortho-/meta-/pararatio of 1:6:4 under Ritter's protocol, whereas van Gemmeren and co-workers report 58% yield and Yu's group reported 56% yield, respectively.…”

Section: C−h Olefinationmentioning

confidence: 99%

Toolbox for Distal C–H Bond Functionalizations in Organic Molecules

et al. 2021

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Transition-metal-catalyzed C−H activation has developed a contemporary approach to the omnipresent area of retrosynthetic disconnection. Scientific researchers have been tempted to take the help of this methodology to plan their synthetic discourses. This paradigm shift has helped in the development of industrial units as well, making the synthesis of natural products and pharmaceutical drugs step-economical. In the vast zone of C−H bond activation, the functionalization of proximal C−H bonds has gained utmost popularity. Unlike the activation of proximal C−H bonds, the distal C−H functionalization is more strenuous and requires distinctly specialized techniques. In this review, we have compiled various methods adopted to functionalize distal C−H bonds, mechanistic insights within each of these procedures, and the scope of the methodology. With this review, we give a complete overview of the expeditious progress the distal C−H activation has made in the field of synthetic organic chemistry while also highlighting its pitfalls, thus leaving the field open for further synthetic modifications.

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Photoinduced regioselective olefination of arenes at proximal and distal sites

Saha¹,

Guin²,

Ali³

et al. 2020

Preprint

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The Fujiwara-Moritani reaction has had a profound contribution in the emergence of contemporary C-H activation protocols. Despite the applicability of the traditional approach in different fields, the associated reactivity and regioselectivity issues had rendered it redundant. The revival of this exemplary reaction requires the development of a mechanistic paradigm that would have simultaneous control on both the reactivity and regioselectivity. Often high thermal energy required to promote olefination leads to multiple site functionalization. To this aim we established a photoredoxcatalytic system constituting a merger of palladium/organo-photocatalyst that forges oxidative olefination in an explicit regioselective fashion of diverse arenes and heteroarenes. Visible light plays a significant role in executing ‘regio-resolved’ Fuijiwara-Moritani reaction without the requirement of silver salts and thermal energy. The catalytic system is also amenable towards proximal and distal olefination aided by respective directing groups (DGs), which entails the versatility of the protocol in engaging the entire spectrum of C(sp2)-H olefination. Furthermore, streamlining the synthesis of natural products, chiral molecules, drugs and diversification through late-stage functionalizations underscore the importance of this sustainable protocol. The photoinduced attainment of this regioselective transformation is mechanistically established through control reactions, kinetic studies and theoretical calculations.

show abstract

Dual Ligand-Enabled Nondirected C–H Cyanation of Arenes

Cited by 3 publications

References 7 publications

Photoinduced Regioselective Olefination of Arenes at Proximal and Distal Sites

Photoinduced Regioselective Olefination of Arenes at Proximal and Distal Sites

Toolbox for Distal C–H Bond Functionalizations in Organic Molecules

Photoinduced regioselective olefination of arenes at proximal and distal sites

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