Free-Radical Carbonylation by TTMSS Mediated Process

Ryu, Ilhyong; Hasegawa, Megumi; Kurihara, Akio; Ogawa, Akira; Tsunoi, Shinji; Sonoda, Noboru

doi:10.1055/s-1993-22381

Cited by 53 publications

(32 citation statements)

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“…For example, the azobis(isobutyronitrile) (AIBN) initiated reaction of (E)-1-iodo-1-octene with carbon monoxide in the presence of tris(trimethylsilyl)silane (TTMSS) 19 gave 4-oxo-5-dodecenenitrile in 57% yield (Scheme 9). 10 Only the E-form of the product was obtained in this case. A similar reaction using (Z)-1-iodo-1-octene also gave the same E product.…”

Section: T-bumentioning

confidence: 98%

“…8 Work in our laboratories has also found that -ketenyl radicals are most likely generated during radical carbonylation processes that involve vinyl radicals. [10][11][12][13] In this Account, we describe unique synthetic methods for carbonyl compounds based on the carbonylation of vinyl radicals, in which ,-unsaturated acyl radicals and -ketenyl radicals play a key role. We also describe some of our recent computational studies based on ab-initio and DFT calculations, which predict that ,-unsaturated acyl and -ketenyl radicals are distinct species, rather than canonical forms of a common radical.…”

Section: Introductionmentioning

confidence: 99%

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Carbonylative Approaches to α,β-Unsaturated Acyl Radicals and α-Ketenyl Radicals. Their Structure and Applications in Synthesis

Ryu¹,

Uenoyama²,

Matsubara³

2006

Bulletin of the Chemical Society of Japan

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The carbonylation of vinyl radicals gives ,-unsaturated acyl radicals. This transformation was successfully applied to tandem radical reactions, resulting in assembling three and four components. In these reactions, both halogen abstraction from vinyl halides and hetero atom radical additions to alkynes are used to generate the parent vinyl radicals. Ab initio calculations and density functional methods predict that ,-unsaturated acyl radicals and the isomeric -ketenyl radicals are not canonical forms, but are isomeric species that undergo interconversion. Calculations also indicate that ,-unsaturated acyl radicals are more stable than -ketenyl radicals, whereas -ketenyl radicals containing a heteroatom, such as Si, Ge, and Sn, at -position are more stable than the corresponding ,-unsaturated acyl radicals. This represents a promising resource for developing new synthetic applications that involve the use of the -ketenyl radicals. Indeed, following the prediction by calculation, we succeeded in trapping of a tin-attached -ketenyl radical by imines and amines in an intramolecular fashion. We were also able to achieve the intermolecular trapping of -ketenyl radicals, providing a new method for alkyne carbonylation by hybrid radical/ ionic reactions.

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Section: T-bumentioning

confidence: 98%

Section: Introductionmentioning

confidence: 99%

Carbonylative Approaches to α,β-Unsaturated Acyl Radicals and α-Ketenyl Radicals. Their Structure and Applications in Synthesis

Ryu¹,

Uenoyama²,

Matsubara³

2006

Bulletin of the Chemical Society of Japan

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“…Unsymmetrical ketones can be synthesized by the formal double alkylation of carbon monoxide [21] in which the three-component coupling of alkyl halides, carbon monoxide, and electron-deficient alkenes is carried out using tributyltin hydride as a radical chain mediator (Scheme 6.13) [22]. The use of a slower radical mediator such as (TMS) 3 SiH [23] has subsequently proven to be superior to tribu- tyltin hydride for this type of reaction, since the reaction can be conducted using smaller amounts of alkenes along with lower CO pressures.…”

Section: Multicomponent Coupling Reactions Mediated By Group 14 Radicalsmentioning

confidence: 99%

Free‐Radical‐Mediated Multicomponent Coupling Reactions

Tojino

Ryu

2005

Multicomponent Reactions

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“…The carbonylation of functionalized alkenes in the presence of alkyl bromides and iodides under radical producing conditions gives good yields ofˇ-functionalized ketones (equation 95) 369,370 . These compounds may be formed with cyano, ester and aldehyde groups attached directly to the alkene.…”

Section: A Carbonylation and Related Reactionsmentioning

confidence: 99%