Gold-Catalyzed Double Spirocyclization of 3-Ene-1,7-diyne Esters to Dispiroheterocycles

Chen, Jichao; Liu, Zhen; León Rojas, Andrés Felipe; Rao, Weidong; Chan, Philip Wai Hong

doi:10.1021/acs.orglett.4c00884

Org. Lett.

2024

DOI: 10.1021/acs.orglett.4c00884

|View full text |Cite

Gold-Catalyzed Double Spirocyclization of 3-Ene-1,7-diyne Esters to Dispiroheterocycles

Jichao Chen,

Zhen Liu,

Andrés Felipe León Rojas

et al.

Abstract: A synthetic method to prepare dispiroheterocycles containing two all-carbon quaternary centers efficiently that relies on the gold(I)-catalyzed double spirocyclization of 3-ene-1,7-diyne esters is described. The suggested mechanism delineates a rare example of a dispirocyclization featuring two 1,n-acyloxy shifts comprising a 1,3-acyloxy migration and an interrupted 1,5-acyl migration that was achieved with the assistance of residual water in the reaction media.

Help me understand this report

Search citation statements

Order By: Relevance

Paper Sections

Select...

Citation Types

Supporting

Mentioning

Contrasting

Year Published

2024

Publication Types

Select...

Article5

Relationship

Self Cite0

Independent5

Authors

Journals

Cited by 5 publications

References 41 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

Ruthenium and Iodine Anion Cocatalyzed Cascade Dihalogenation and Cyclization of Internal Alkyne-Tethered Cyclohexadienones with 1,2-Dihaloethanes

Huang,

Yi,

Bai

et al. 2024

J. Org. Chem.

View full text Add to dashboard Cite

Ruthenium and Iodine Anion Cocatalyzed Cascade Dihalogenation and Cyclization of Internal Alkyne-Tethered Cyclohexadienones with 1,2-Dihaloethanes

Huang,

Yi,

Bai

et al. 2024

J. Org. Chem.

View full text Add to dashboard Cite

Gold(I)-Catalyzed Rautenstrauch/Hetero-Diels–Alder/Retro-aza-Michael Cascade Reaction for the Synthesis of α-Hydrazineyl-2-cyclopentenones

Scarpi,

Capanni,

Visi

et al. 2024

J. Org. Chem.

View full text Add to dashboard Cite

A one-pot synthesis of ring-fused, α-hydrazineyl-2-cyclopentenone derivatives is achieved by a gold(I)-catalyzed Rautenstrauch/hetero Diels–Alder/ring opening tandem reaction of suitable propargyl esters. By mixing the latter with a dialkylazodicarboxylate in the presence of a gold(I) catalyst, the 1,2-acyloxy migration/cyclization process (Rautenstrauch reaction) leads to cyclopentadienyl ester intermediates which are trapped by the heterodienophile present in situ. This provides strained intermediates which spontaneously undergo highly regioselective ring opening by a retro aza-Michael reaction promoted by the gold(I) catalyst, eventually yielding the target compounds. Six- and seven-membered ring-fused cyclopentenones bearing a pendant α-hydrazineyl moiety can be obtained in moderate to excellent yield (50–98%) by this approach, with a minimal erosion of the initial optical purity when using enantioenriched substrates.

show abstract

DFT Investigation on Palladium-Catalyzed [2 + 2 + 1] Spiroannulation between Aryl Halides and Alkynes: Mechanism, Base Additive Role, and Solvent and Ligand Effects

Tan,

Bai,

Shi

et al. 2024

J. Phys. Chem. A

View full text Add to dashboard Cite

Transition metal-catalyzed spiroannulations are practical strategies for constructing spirocyclic skeletons of pharmaceutical and biological significance, yet the microscopic mechanism still lacks in-depth explorations. Here, the palladiumcatalyzed [2 + 2 + 1] spiroannulation between aryl halides and alkynes was studied by employing the density functional theory (DFT) method. Based on comprehensive explorations on a couple of possible reaction pathways, it is found that the reaction probably experiences C−I oxidative addition, alkyne migration insertion, Cs 2 CO 3 -assisted aryl C−H activation, C−Br bond oxidative addition, C−C coupling, arene dearomatization and reductive elimination in sequence and leads to the formation of the spiro[4,5]decane pentacyclic product (P) ultimately. Among these, the C−Br bond oxidative addition step acts as the rate-determining step (RDS) of the whole reaction, featuring a practical free energy barrier of 32.4 kcal•mol −1 at 130 °C. Computationally predicted kinetics such as half-life transferred from the RDS step's barrier on the optimal reaction pathway (1.2 × 10 1 h) coincides well with corresponding experimental results (91% yield of the spiro[4,5]decane pentacyclic product P after reacting 10 h at 130 °C). In addition, theoretical predictions regarding the solvent/ ligand effects and base additive role in the reaction, rationalized by distortion−interaction/natural population/noncovalent interaction analyses, are also in good agreement with experimental data and trend. This good agreement between experiment and theory makes sense for new designations and further experimental improvements of such Pd-catalyzed transformations.

show abstract

scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.

Contact Info

customersupport@researchsolutions.com

10624 S. Eastern Ave., Ste. A-614

Henderson, NV 89052, USA

This site is protected by reCAPTCHA and the Google Privacy Policy and Terms of Service apply.

Blog Terms and Conditions API Terms Privacy Policy Contact Cookie Preferences Do Not Sell or Share My Personal Information

Made with 💙 for researchers

Part of the Research Solutions Family.

Gold-Catalyzed Double Spirocyclization of 3-Ene-1,7-diyne Esters to Dispiroheterocycles

Cited by 5 publications

References 41 publications

Ruthenium and Iodine Anion Cocatalyzed Cascade Dihalogenation and Cyclization of Internal Alkyne-Tethered Cyclohexadienones with 1,2-Dihaloethanes

Ruthenium and Iodine Anion Cocatalyzed Cascade Dihalogenation and Cyclization of Internal Alkyne-Tethered Cyclohexadienones with 1,2-Dihaloethanes

Gold(I)-Catalyzed Rautenstrauch/Hetero-Diels–Alder/Retro-aza-Michael Cascade Reaction for the Synthesis of α-Hydrazineyl-2-cyclopentenones

DFT Investigation on Palladium-Catalyzed [2 + 2 + 1] Spiroannulation between Aryl Halides and Alkynes: Mechanism, Base Additive Role, and Solvent and Ligand Effects

Contact Info

Product

Resources

About