Sulfurane [S(IV)]-Mediated Fusion of Benzynes Leads to Helical Dibenzofurans

Review Chemistry, Multidisciplinary

Hexadehydro-Diels-Alder Reaction: Benzyne Generation via Cycloisomerization of Tethered Triynes

Lucas L. Fluegel et al.

Summary: The HDDA reaction is a thermal cyclization process that generates highly functionalized benzenoid products, attracting attention for its versatility and customizable nature among researchers.

CHEMICAL REVIEWS (2021)

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Review Chemistry, Multidisciplinary

Chiroptical Properties of Symmetric Double, Triple, and Multiple Helicenes

Tadashi Mori

Summary: This review focuses on the chiroptical properties of multiple helicenes, with an emphasis on the impact of the arrangement of multiple helices on the chiroptical responses. Although the number of multiple helicenes reported is limited, insights into the design principle for advanced chiroptical materials through the proper arrangement of multiple helices are provided.

CHEMICAL REVIEWS (2021)

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Article Chemistry, Organic

o-Quinone Methides and o-Quinone Sulfides via Arynes: Synthesis of Ortho-Disubstituted Arenes and Heterocycles

Abhilash Sharma et al.

Summary: In recent years, o-quinone methides and o-quinone sulfides have been widely recognized as reactive intermediates in the synthesis of diversely functionalized ortho-disubstituted arenes and heterocycles. This synopsis provides a comprehensive overview on the potential applications of these compounds in the one-pot synthesis of ortho-disubstituted arenes and heterocycles via arynes, highlighting their importance in organic synthesis.

JOURNAL OF ORGANIC CHEMISTRY (2021)

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Review Chemistry, Multidisciplinary

o-Silylaryl Triflates: A Journey of Kobayashi Aryne Precursors

Jiarong Shi et al.

Summary: Arynes are highly active organic intermediates used in the rapid synthesis of substituted arenes, with o-silylaryl triflates being the most frequently employed precursors. The resurgence in aryne chemistry over the past 20 years is largely attributed to the widespread use of Kobayashi's method, which involves fluoride-induced removal of the TMS group with concomitant departure of its ortho OTf group. This review provides an overview of the history, achievements, and applications of Kobayashi's method in the synthesis of natural products, bioactive molecules, and polycyclic aromatic hydrocarbons.

CHEMICAL REVIEWS (2021)

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Article Chemistry, Multidisciplinary

Aryne 1,2,3,5-Tetrasubstitution Enabled by 3-Silylaryne and Allyl Sulfoxide via an Aromatic 1,3-Silyl Migration

Jiarong Shi et al.

Summary: An unprecedented aryne 1,2,3,5-tetrasubstitution was achieved through a reaction involving 3-silylbenzyne and aryl allyl sulfoxide. The mechanism includes regioselective aryne insertion into the S=O bond, [3,6]-sigmatropic rearrangement, and thermal aromatic 1,3-silyl migration cascade.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Article Chemistry, Multidisciplinary

Benzyne 1,2,4-Trisubstitution and Dearomative 1,2,4-Trifunctionalization

Jiarong Shi et al.

Summary: Both 1,2,4-trisubstitution and dearomative 1,2,4-trifunctionalization of benzyne were successfully achieved from sulfoxides bearing a penta-2,4-dien-1-yl moiety. These cascade transformations involve benzyne insertion into the S = O bond and a rare regiospecific anionic [4,5]-sigmatropic rearrangement, leading to the formation of C-O, C-S, and C-C bonds on the C1-, C2-, and C4-position of a benzene ring, respectively. This study introduces new cascade benzyne reaction modes that include distal C-H bond functionalization and dearomatization.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Article Chemistry, Multidisciplinary

Could London Dispersion Force Control Regioselective (2+2) Cyclodimerizations of Benzynes? YES: Application to the Synthesis of Helical Biphenylenes

Takashi Ikawa et al.

Summary: In recent years, it has been discovered that London dispersion interactions play an important role in controlling the regio- and stereo-selectivity of reactions. These interactions are dominant in selective catalysis, while repulsive steric interactions are predominant in noncatalytic reactions. A novel method utilizing London dispersion interactions has been developed for the synthesis of proximal biphenylenes, which have potential applications in ligands, catalysts, and medicines.

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY (2021)

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Article Chemistry, Multidisciplinary