Theoretical Studies of Allene Synthesis through Cadmium Iodide‐Mediated Allenylation of Terminal Alkynes

Enolates formed from 1‐phenyl‐5‐tetrazolyl β‐ketosulfones containing a tetrasubstituted α carbon centre undergo elimination to allenes with up to four substituents at the cumulene unit when treated with a weak base (phenolate) in DMSO at room temperature. The reaction is completely regioselective for allene vs diene formation in nearly all investigated cases and it proceeds with central‐to‐axial chirality transfer.

show abstract

Stereospecific Synthesis of Allenes from β‐Ketosulfones

Wasilewska-Rosa

Kisiel

Tkaczyk

et al. 2023

Adv Synth Catal

View full text Add to dashboard Cite

show abstract

Room Temperature Allenation of Terminal Alkynes with Aldehydes

Xiao

Cui

et al. 2021

Angewandte Chemie

Self Cite

View full text Add to dashboard Cite

A gold-catalyzed room temperature allenation of terminal alkynes (ATA) with aldehydes affording 1,3-disubstituted allenes with diverse functional groups has been developed by identifying a gold(I) catalyst and an amine. The practicality of this reaction has been demonstrated by a ten gram-scale synthesis and the synthetic potentials have been demonstrated via various transformations and formal total synthesis of (À)-centrolobine. Mechanistic studies revealed that the gold catalyst, the aldehyde effect, the fluoroalkyl hydroxyl solvent (TFE or HFIP) and the structure of amine are vital in this room temperature ATA reaction.

show abstract

Enantioselective Allenation of Terminal Alkynes Catalyzed by Copper Halides of Mixed Oxidation States and Its Application to the Total Synthesis of Scorodonin

Yao

et al. 2021

Angewandte Chemie

Self Cite

View full text Add to dashboard Cite

Naturally occurring conjugated allenynes are of general interest owing to their potent and various biological activities. The 1,5‐H transfer of alka‐1,4‐diyn‐3‐yl amines would be one of the most straightforward yet challenging approaches to such compounds since, in principle, two regioisomers may be formed involving two C−C triple bonds. Herein, a catalytic recipe of copper halides with mixed oxidation states, i.e., CuCl/CuBr2, has been identified to address the issues of the side reaction of conjugate addition and the selectivity of 1,5‐H transfer of alka‐1,4‐diyn‐3‐yl amines in EATA (enantioselective allenation of terminal alkynes) reaction involving 2‐alkynals. This method provided various allenynes with excellent enantioselectivities, and was also applied to the first highly enantioselective total synthesis of natural product scorodonin. Mechanistic studies and DFT calculations elucidated the regioselectivity for the observed 1,5‐H transfer.

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.

Theoretical Studies of Allene Synthesis through Cadmium Iodide‐Mediated Allenylation of Terminal Alkynes

Cited by 8 publications

References 97 publications

Stereospecific Synthesis of Allenes from β‐Ketosulfones

Stereospecific Synthesis of Allenes from β‐Ketosulfones

Room Temperature Allenation of Terminal Alkynes with Aldehydes

Enantioselective Allenation of Terminal Alkynes Catalyzed by Copper Halides of Mixed Oxidation States and Its Application to the Total Synthesis of Scorodonin

Contact Info

Product

Resources

About