Facile and highly selective silylation of vinylpyridines at the β-olefinic carbon by magnesium-promoted reduction

Zhang, Tianyuan; Zhang, Zeyu; Nishiyama, Yutaro; Maekawa, Hirofumi

doi:10.1016/j.tet.2016.03.042

Cited by 13 publications

(7 citation statements)

References 43 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…11a,36 We envisioned a complementary strategy for transition-metal-free hydrosilylation via electrochemistry by intercepting carbanion Int-2 with an appropriate proton source. 37 Indeed, when weakly acidic acetonitrile was used as the solvent in lieu of THF, hydrosilylation proceeded as the predominant pathway with little competitive disilylation. Thus, a collection of hydrosilylated products were synthesized from conjugated alkenes, alkynes, and chlorosilanes (Scheme 5B).…”

mentioning

confidence: 99%

An Electroreductive Approach to Radical Silylation via the Activation of Strong Si–Cl Bond

et al. 2020

View full text Add to dashboard Cite

The construction of C(sp3)–Si bonds is important in synthetic, medicinal, and materials chemistry. In this context, reactions mediated by silyl radicals have become increasingly attractive but methods for accessing these intermediates remain limited. We present a new strategy for silyl radical generation via electroreduction of readily available chlorosilanes. At highly biased potentials, electrochemistry grants access to silyl radicals through energetically uphill reductive cleavage of strong Si–Cl bonds. This strategy proved to be general in various alkene silylation reactions including disilylation, hydrosilylation, and allylic silylation under simple and transition-metal-free conditions.

show abstract

mentioning

confidence: 99%

An Electroreductive Approach to Radical Silylation via the Activation of Strong Si–Cl Bond

et al. 2020

View full text Add to dashboard Cite

show abstract

“…35 This hypothesis was first validated in the anion probe experiment and was further expanded to various other substrates (Scheme 5C). Importantly, this system allowed us to expand the scope of electroreductive silylation from conjugated alkenes (34,54) to simple alkenes (55-56, 59, 61). In addition to allylethers, even allylic alcohols (63-65) can be directly used as starting materials presumably via the initial formation of a TMS-ether.…”

Section: Int-1mentioning

confidence: 99%

An Electroreductive Approach to Silyl Radical Chemistry via Strong Si–Cl Bond Activation

Lu¹,

Siu²,

Lai³

et al. 2020

Preprint

View full text Add to dashboard Cite

The construction of C(sp<sup>3</sup>)–Si bonds is important in synthetic, medicinal, and materials chemistry. In this context, reactions mediated by silyl radicals have become increasingly attractive but methods for accessing these intermediates remain limited. We present a new strategy for silyl radical generation via electroreduction of readily available chlorosilanes. At highly biased potentials, electrochemistry grants access to silyl radicals through energetically uphill reductive cleavage of strong Si–Cl bonds. This strategy proved to be general in various alkene silylation reactions including disilylation, hydrosilylation, and allylic silylation under simple and transition-metal-free conditions.

show abstract

“…11a,33 We envisioned a complementary strategy for transition-metal-free hydrosilylation via electrochemistry by intercepting carbanion Int-2 with an appropriate proton source. 34 Indeed, when weakly acidic acetonitrile was used as the solvent in lieu of THF, hydrosilylation proceeded as the predominant pathway with little competitive disilylation. Thus, a collection of hydrosilylated products were synthesized from conjugated alkenes, alkynes, and chlorosilanes (Scheme 5B).…”

Section: Scheme 4 Proposed Mechanismmentioning

confidence: 99%

“…35 This hypothesis was first validated in the anion probe experiment and was further expanded to various other substrates (Scheme 5C). Importantly, this system allowed us to expand the scope of electroreductive silylation from conjugated alkenes (34,54) to simple alkenes (55-56, 61). In addition to allylethers, even allylic alcohols (63-65) can be directly used as starting materials presumably via the initial formation of a TMS-ether.…”

Section: Scheme 4 Proposed Mechanismmentioning

confidence: 99%

An Electroreductive Approach to Silyl Radical Chemistry via Strong Si–Cl Bond Activation

Lu¹,

Siu²,

Lai³

et al. 2020

Preprint

View full text Add to dashboard Cite

show abstract

Facile and highly selective silylation of vinylpyridines at the β-olefinic carbon by magnesium-promoted reduction

Cited by 13 publications

References 43 publications

An Electroreductive Approach to Radical Silylation via the Activation of Strong Si–Cl Bond

An Electroreductive Approach to Radical Silylation via the Activation of Strong Si–Cl Bond

An Electroreductive Approach to Silyl Radical Chemistry via Strong Si–Cl Bond Activation

An Electroreductive Approach to Silyl Radical Chemistry via Strong Si–Cl Bond Activation

Contact Info

Product

Resources

About