Palladium‐Catalyzed Silylcyanation of Ynamides: Regio‐ and Stereoselective Access to Tetrasubstituted 3‐Silyl‐2‐Aminoacrylonitriles

We have developed a palladium-catalyzed addition of a CÀ Si bond of acylsilanes across a range of unactivated allenes. The reaction proceeds with complete regioselectivity, in which a silyl group binds to the central carbon of the allene, allowing for the straightforward access to functionalized alkenylsilane derivatives.Organosilicon compounds are essential components in diverse disciplines, encompassing synthetic organic, [1a-c] polymers, materials, [1d,e] bioorganic and medicinal chemistry. [1f,g] The most powerful and most widely used method, both commercially and in the laboratory, for their synthesis involves the transition metal-catalyzed hydrosilylation of unsaturated hydrocarbons, in which a HÀ Si bond is added across alkenes or alkynes. [2] If a CÀ Si bond in organosilanes could be added to unsaturated hydrocarbons in a similar manner, it would be a method of great value since it would allow access to elaborate organosilicon compounds from simpler organosilicon feedstocks with a 100 % atom economy (Figure 1). [3] However, realizing such an insertion reaction into a CÀ Si bond represents a daunting challenge, because, unlike a HÀ Si bond, the requisite oxidative addition of a CÀ Si bond is an uncommon organometallic process. [4] In fact, the cleavage of a CÀ Si bond by transition metal complexes primarily occurs through transmetallation with complexes bearing an X-type ligand, during which a silicon group is eliminated. [1b,c, 5] Therefore, insertion reactions into a CÀ Si bond, except for those using strained silacyclyes (i.e., silacyclopropanes [6] and silacyclobutanes [7] ), silyl cyanides [8] and intramolecular reactions, have not been reported (Figure 1a). [9,10] The Lewis acid-mediated carbosilylation of allylsilanes and related activated silanes have been reported, but, in such reactions, the CÀ Si bond cleavage occurs via a carbocation intermediate. [11] The photochemical addition of a CÀ Si bond of acylsilanes to activated alkynes has been reported, although the applicable alkynes are limited to acetylenedicarboxylates or intramolecular reactions (Figure 1b). [12] We report herein on the palladiumcatalyzed addition of a CÀ Si bond in acylsilanes across allenes, in which a CÀ C double bond can be functionalized with both acyl and silyl groups (Figure 1c). Narasaka and co-workers reported on the palladiumcatalyzed decarbonylative bis-silylation of dimethyl acetylenedicarboxylate using a bis-silyl ketone, which appears to proceed through the oxidative addition of a CÀ Si bond. [13] We also previously reported on the palladium-catalyzed siloxycyclopropanation of alkenes using acylsilanes, in which the oxidative addition of a CÀ Si bond presumably triggers the generation of a key siloxycarbene-palladium

show abstract

Palladium‐Catalyzed Silylacylation of Allenes Using Acylsilanes

Inagaki

Sakurai

Yamanaka

et al. 2022

Angewandte Chemie

View full text Add to dashboard Cite

show abstract

Palladium‐Catalyzed Silylacylation of Allenes Using Acylsilanes

et al. 2022

View full text Add to dashboard Cite

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.

Palladium‐Catalyzed Silylcyanation of Ynamides: Regio‐ and Stereoselective Access to Tetrasubstituted 3‐Silyl‐2‐Aminoacrylonitriles

Cited by 2 publications

References 93 publications

Palladium‐Catalyzed Silylacylation of Allenes Using Acylsilanes

Palladium‐Catalyzed Silylacylation of Allenes Using Acylsilanes

Palladium‐Catalyzed Silylacylation of Allenes Using Acylsilanes

Contact Info

Product

Resources

About