Gold(I)‐Catalyzed Cycloisomerization of <i>ortho</i>‐(Propargyloxy)arenemethylenecyclopropanes Controlled by Adjacent Substituents at Aromatic Rings

Fang, Wei; Wei, Yin; Tang, Xiang‐Ying; Shi, Min

doi:10.1002/chem.201700600

Cited by 18 publications

(21 citation statements)

References 169 publications

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“…Treatment of sabinol 1 with m -CPBA did not yield the desired epoxide 15 . Rather, the generated epoxide underwent an in situ ring-opening process after the electrophilic attack of the formed m -chlorobenzoic acid, resulting in ester 17 ( Scheme 5 ) [ 44 , 45 , 46 ]. The intermediate epoxide could not be isolated even after applying miscellaneous conditions, such as varying temperature, NaHCO 3 or Na 2 CO 3 , or buffer solutions.…”

Section: Resultsmentioning

confidence: 99%

Stereoselective Syntheses and Application of Chiral Bi- and Tridentate Ligands Derived from (+)-Sabinol

et al. 2018

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A library of bidentate diols, as well as tridentate triols and aminodiols, derived from (+)-sabinol, was synthesized in a stereoselective manner. Sabinol was transformed into allylic trichloroacetamide via Overman rearrangement of the corresponding trichloroacetimidate. After changing the protecting group to Boc, the enamine was subjected to stereospecific dihydroxylation with OsO4/NMO, resulting in the (1R,2R,3R,5R)-aminodiol diastereomer. The obtained primary aminodiol was transformed to a secondary analogue. The ring closure of the N-benzyl-substituted aminodiol with formaldehyde was investigated and regioselective formation of the spiro-oxazolidine ring was observed. Hydroboration or dihydroxylation of sabinol or its benzyl ether with OsO4/NMO resulted in the formation of sabinane-based diols and triols following a highly stereospecific reaction. Treatment of sabinol with m-CPBA afforded O-benzoyl triol as a diastereoisomer of the directly dihydroxylated product, instead of the expected epoxy alcohol. The resulting aminodiols, diol, and triols were applied as chiral catalysts in the reaction of diethylzinc and benzaldehyde from moderate to good selectivity.

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Section: Resultsmentioning

confidence: 99%

Stereoselective Syntheses and Application of Chiral Bi- and Tridentate Ligands Derived from (+)-Sabinol

et al. 2018

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“…Furthermore, we also reported a gold(I)‐catalyzed cycloisomerization of MCP‐containing alkynes 101 , affording two different types of products 104 and 105 , controlled jointly by electronic and steric effects of the adjacent substituents (Scheme a) . The formation of 104 resulted from the higher electron density on the C2 atom when R 1 was a tert ‐butyl ( t Bu) or tert ‐amyl ( t Am) group.…”

Section: Transformations Of Facpsmentioning

confidence: 96%

“…2019, 25,7591 -7606 www.chemeurj.org tronic and steric effects of the adjacent substituents (Scheme 22 a). [28] The formation of 104 resultedf rom the higher electron density on the C2 atom when R 1 was a tertbutyl (tBu) or tert-amyl (tAm) group. Therefore, the alkyne moietyw as firstly activated by the gold catalyst, followed by nucleophilic attack by the aryl ring.…”

Section: Ring-opening Reactions With Proximal Càcb Ond Cleavagementioning

confidence: 99%

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The Construction of Molecular Complexity from Functionalized Alkylidenecyclopropanes (FACPs)

Shi

2019

Chemistry A European J

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As a special family of cyclopropanes, alkylidenecyclopropanes (ACPs), exhibit outstanding physical and chemical activities, which provide opportunities to participate in fascinating chemical transformations to access cyclopropane‐containing units without ring‐opening processes and other unavailable compounds through conventional routes with ring‐opening processes owing to their strain‐driven reactivity and synthetic accessibility. Nowadays, intramolecular reactions of methylenecyclopropanes (MCPs) or ACPs with adjacent functionalities have emerged as a powerful synthetic protocol for the construction of a variety of polycyclic and heterocyclic compounds with different sized skeletons through catalytic methods. Recently, we put forward the concept of functional alkylidenecyclopropanes (FACPs) and in this Minireview, we will summarize the reactions of FACPs after 2016 including several important early works from three aspects: 1) reactions with distal C−C bond cleavage, 2) reactions with proximal C−C bond cleavage (including ring‐expansion reactions), and 3) reactions without C−C bond cleavage.

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“…Substrates lacking the phenolic ether failed to induce any cyclization reaction (Figure b) . Shi et al further elaborated this approach to assemble chromene and dihydrobenzofuran by introducing the cyclopropane moiety to the olefin …”

Section: Synthesis Of Bio‐relevant Small To Medium Ring‐heterocyclesmentioning

confidence: 99%

Gold(I) Catalyzed Enyne Cycloisomerization – A Roadmap to Privileged Heterocyclic Scaffolds

Lee

Kumar

2018

Israel Journal of Chemistry

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Gold(I) catalyzed cycloisomerization reaction is one of the key transformations that remain underexplored to build molecular diversity and complexity. In this review, we summarize synthesis endeavors where enyne cycloisomerization chemistry was utilized to form structurally intriguing as well as biologically relevant heterocyclic scaffolds. To this goal, most of the efforts tend to exploit gold carbene type intermediates, often supporting a cyclopropane ring and transform them into new scaffolds. Various examples have been grouped together to highlight the role of presence or absence of external heteroatom nucleophiles in modulating reactive intermediates into novel molecular frameworks. The last section is devoted to the emerging role of gold(I) catalyzed cycloisomerization reactions in driving the divergent synthesis approaches wherein a common substrate can be transformed into distinct molecular scaffolds by merely varying reaction conditions or gold complexes.

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Gold(I)‐Catalyzed Cycloisomerization of ortho‐(Propargyloxy)arenemethylenecyclopropanes Controlled by Adjacent Substituents at Aromatic Rings

Cited by 18 publications

References 169 publications

Stereoselective Syntheses and Application of Chiral Bi- and Tridentate Ligands Derived from (+)-Sabinol

Stereoselective Syntheses and Application of Chiral Bi- and Tridentate Ligands Derived from (+)-Sabinol

The Construction of Molecular Complexity from Functionalized Alkylidenecyclopropanes (FACPs)

Gold(I) Catalyzed Enyne Cycloisomerization – A Roadmap to Privileged Heterocyclic Scaffolds

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