Dearomative logic in natural product total synthesis

Huck, Christopher J.; Boyko, Yaroslav; Šarlah, David

doi:10.1039/d2np00042c

Cited by 45 publications

(26 citation statements)

References 462 publications

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“…One of the most attractive features of these caged natural products, in my opinion, are their highly congested tetracyclo [5.3.3.0 4,9 .0 4,12 ]-tridecane core structure that possess two contiguous bicyclo[2.2.2]octane motifs. Extensive efforts from our community have culminated in several total syntheses of atropurpuran as well as arcutine-type diterpenoid alkaloids.…”

Section: Figure 1 Atropurpuran and Arcutine-type Alkaloidsmentioning

confidence: 99%

Total Synthesis of the Caged Diterpenoid Atropurpuran

2022

Synlett

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Section: Figure 1 Atropurpuran and Arcutine-type Alkaloidsmentioning

confidence: 99%

Total Synthesis of the Caged Diterpenoid Atropurpuran

2022

Synlett

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“…1 A number of aromatic dienes, such as furan, and fused (hetero)arenes with modest resonance energies readily participate in dearomative cycloadditions. 2 However, intermolecular cycloadditions 3 of benzene rings that are neither strained 4 nor electronically 5 activated seldom occur under pressures and temperatures that are conducive to their application in organic synthesis. 6 Notable exceptions include cycloadditions carried out photochemically, 7 through prior coordination of the arene to a transition metal complex, 8 or else with exceptionally reactive reaction partners such as activated arynes, 9 and carbenes or metal carbenoids.…”

Section: Introductionmentioning

confidence: 99%

Skeletal Transformation of Unactivated Arenes Enabled by a Low-Temperature Dearomative (3+2) Cycloaddition

Pradhan

Mohammadi

Bouffard

2023

Preprint

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Simple aromatic compounds like benzene are abundant feedstocks, for which the preparation of derivatives chiefly begins with electrophilic substitution reactions, or less frequently reductions. Their high stability makes them particularly reluctant to participate in cycloadditions under ordinary reaction conditions. Here we demonstrate the exceptional ability of 1,3-diaza-2-azoniaallene cations to undergo formal (3+2) cycloadditions with unactivated benzene derivatives, below room temperature, to provide thermally stable dearomatized adducts on a multi-gram scale. The cycloaddition, which tolerates polar functional groups, activates the ring toward further elaboration. On treatment with dienophiles the cycloadducts undergo a (4+2) cycloaddition-cycloreversion cascade to yield substituted or fused arenes, including naphthalene derivatives. The overall sequence results in the transmutation of arenes through an exchange of the ring's carbons: a two-carbon fragment from the original aromatic ring is replaced with another from the incoming dienophile, introducing an unconventional disconnection for the synthesis of ubiquitous aromatic building blocks. Applications of this two-step sequence to the preparation of substituted acenes, isotopically labeled molecules, and medicinally relevant compounds are demonstrated.

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“…Recently, two articles covering key transformations mediated by iodanes in total syntheses were published. First, a general review by Sarlah and coworkers depicts dearomative logic in total synthesis, 6 including reactions mediated by iodanes. Second, Wang focused on the use of iodane( iii ) in some total syntheses.…”

Section: Introductionmentioning

confidence: 99%