Regioselective Synthesis of Polycyclic and Heptagon‐embedded Aromatic Compounds through a Versatile π‐Extension of Aryl Halides

Fu, Wai Chung; Wang, Zheng; Chan, Wesley Ting Kwok; Lin, Zhenyang; Kwong, Fuk Yee

doi:10.1002/anie.201703551

Cited by 122 publications

(51 citation statements)

References 88 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Formation of 7-and 8-Membered Rings by Pd-Catalyzed C-H Bond ArylationIn 2017, during their investigations on the synthesis of phenanthrene derivatives via palladiumcatalyzed three-component cross-coupling of aryl halides, 2-haloarylcarboxylic acids, and norbornadiene, Kwong and co-workers discovered that the use of 8-bromo-1-naphthoic acid as 2-haloarylcarboxylic acid source allowed the one-pot synthesis of unique heteroatom-fused heptagonal polyaromatics (Scheme 63) 100. Notability, such 7-membered ring PAHs or similar one are challenging to synthesize by traditional methods due to multi-steps synthetic approches.This π-extension reaction involves oxidative addition of C-I bond to Pd(0), norbornadiene insertion followed by an ortho-phenyl C-H bond activation via a Catellani process, then oxidative addition of C-Br bond and subsequent decarboxylation of the carboxyl group lead to the formation of the desired products after retro-Diels-Alder reaction.…”

mentioning

confidence: 99%

Application of Palladium-Catalyzed C(sp2)–H Bond Arylation to the Synthesis of Polycyclic (Hetero)Aromatics

Hagui

Doucet

2019

Chem

122

View full text Add to dashboard Cite

Recently, the use of the palladium-catalyzed inter-and/or intra-molecular C-H bond arylations in the building of various π-extended (hetero)aromatic structures has emerged as a suitable alternative to the previous multi-steps synthesis. Such new methodology even allowed to prepare unprecedented π-extended molecules owing a perfect control of the reaction sites. This review gives an overview of various synthesis of Polycyclic Aromatic Hydrocarbons (PAHs) and PolyCyclic Heteroaromatics (PCHs) with planar, bowl-shaped, and helical structures prepared in high efficiency and selectivity via Pd-catalyzed C-H bond arylations. Bigger Picture Recently, π-extended compounds such as Polycyclic Aromatic Hydrocarbons (PAHs) and PolyCyclic Heteroaromatics (PCHs) have found important applications in the preparation of optoelectronic devices. The degree of π-extension, the topology of the ring fusion, and the periphery of such molecules are essential factors to control their electronic properties at a molecular level. The traditional approach to prepare nanographenes and heteroatom-doped nanographenes relies on Scholl reaction. However, such methodology suffers from limitations such as functional group compatibility. Catalysis plays a pivotal role in the discovery of new transformations enabling the synthesis of novel molecules, including organic materials. Among various catalytic transformations, Pd-catalyzed C-H bond arylation has emerged as an important tool for the construction of well-decorated polycyclic (hetero)aromatic molecules. Such direct approaches have a considerable impact on the synthesis of PAHs and PCHs by shortening the synthetic scheme and also providing a momentous opportunity to design novel structures. eTOC Blurb: This review highlights the potential of Pd-catalyzed C-H bond arylation for the synthesis of π-extended compounds that include

show abstract

mentioning

confidence: 99%

Application of Palladium-Catalyzed C(sp2)–H Bond Arylation to the Synthesis of Polycyclic (Hetero)Aromatics

Hagui

Doucet

2019

Chem

122

View full text Add to dashboard Cite

show abstract

“…Though this strategy was superior to previous methods in terms of mildness of the reaction conditions, it had a limited substrate scope and relatively low reaction efficiency. Very recently, Fuk Yee Kwong and co-workers (Scheme 1) developed a straightforward one pot π-extension method using norbornadiene instead of norbornene as directing group to afford the phenanthrenes [11]. However, ortho -haloaryl carboxylic acids employed in this approach had low reactivity, which needed higher reaction temperatures and longer reaction time.…”

Section: Introductionmentioning

confidence: 99%

A novel and efficient synthesis of phenanthrene derivatives via palladium/norbornadiene-catalyzed domino one-pot reaction

Zhong¹,

Wu²,

Yu³

et al. 2019

Beilstein J. Org. Chem.

View full text Add to dashboard Cite

Herein we report a novel palladium-catalyzed reaction that results in phenanthrene derivatives using aryl iodides, ortho-bromobenzoyl chlorides and norbornadiene in one pot. This dramatic transformation undergoes ortho-C–H activation, decarbonylation and subsequent a retro-Diels–Alder process. Pleasantly, this protocol has a wider substrate range, shorter reaction times and higher yields of products than previously reported methods.

show abstract

“…[6,7] However, the synthesis of such heptagon-embedded PAHs usuallyr equires multiple steps, and direct construction of heptagons from simple and readily available fragments has been rare.R ecently,L in, Kwong, and co-workers disclosed aP d-catalyzedt hree-component annulation reaction of aryl iodide, 8-bromo-1-naphthoic acid, and norbornadiene to afford ah eptagon-containing benzo [4,5]cyclohepta [1,2,3de]naphthalene derivative, in which naphthalene andb enzene rings are linked by a cis-ethenyl (C 2 H 2 )b ridge. [8] Except for this report, annulation approaches to heptagons have been elusive. [9] Herein, we disclose ap alladium-catalyzed heptagonforminga nnulation reaction between 1-halo-8-arylnaphthalene and diarylacetylene.…”

mentioning

confidence: 95%

Pd‐Catalyzed Annulation of 1‐Halo‐8‐arylnaphthalenes and Alkynes Leading to Heptagon‐Embedded Aromatic Systems

Yan

Rahman

Yoshikai

2018

Chemistry A European J

View full text Add to dashboard Cite

Ap alladium-catalyzed heptagon-forming annulation reactionb etween 1-halo-8-arylnaphthalene and diarylacetylenei sreported. The reactioni sp romoted using a catalytic system comprised of Pd(OAc) 2 ,m oderately electron-deficient triarylphosphine P(4-ClC 6 H 4 ) 3 ,a nd Ag 2 CO 3 to afford benzo[4,5]cyclohepta[1,2,3-de]naphthalene derivatives in moderate to good yields, in preference to fluoranthene as ac ompeting byproduct. Twofold annulation can also be achievedt oa ccess an ovel heptagon-embedded polycyclic aromatic hydrocarbon compound.

show abstract

Regioselective Synthesis of Polycyclic and Heptagon‐embedded Aromatic Compounds through a Versatile π‐Extension of Aryl Halides

Cited by 122 publications

References 88 publications

Application of Palladium-Catalyzed C(sp2)–H Bond Arylation to the Synthesis of Polycyclic (Hetero)Aromatics

Application of Palladium-Catalyzed C(sp2)–H Bond Arylation to the Synthesis of Polycyclic (Hetero)Aromatics

A novel and efficient synthesis of phenanthrene derivatives via palladium/norbornadiene-catalyzed domino one-pot reaction

Pd‐Catalyzed Annulation of 1‐Halo‐8‐arylnaphthalenes and Alkynes Leading to Heptagon‐Embedded Aromatic Systems

Contact Info

Product

Resources

About