Acyclic stereocontrol via and electron-transfer process.  Remarkable stereochemical difference between one- and two-electron events

Yamamoto, Yoshinori; Nishii, S.; Ibuka, Toshiro

doi:10.1021/ja00210a061

Cited by 41 publications

(12 citation statements)

References 2 publications

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“…Consequently, in the presence of carboxylic acids used in this study, the mechanism involving protonation of 1 -• at its b-position shown in Scheme 2 should be the predominant pathway. 3 The diastereoselectivity can be explained by the Felkin-Anh-type model where protonation mainly occurs via favored conformation in which the methyl group locates an anticlinal position against the dicyanomethylene moiety of the radical anion 1 -• [21,22]. When dependency of heat of formations of 1 -• on the dihedral angles around the C b -C c bond of 1 -• was calculated by molecular orbital calculation whose basis set was UHF/3-21G, two local minima were found whose structures correspond to the favorable and unfavorable conformations predicted by the FelkinAnh rule (Fig.…”

Section: Resultsmentioning

confidence: 99%

Diastereoselective protonation on a radical anion in the photoallylation and photoreduction of 1,1-dicyano-2-methyl-3-phenyl-1-butene by allyltrimethylsilane

2010

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Section: Resultsmentioning

confidence: 99%

Diastereoselective protonation on a radical anion in the photoallylation and photoreduction of 1,1-dicyano-2-methyl-3-phenyl-1-butene by allyltrimethylsilane

2010

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“…A fluorenone ketyl radical has been detected in an organocuprate reaction of fluorenone. [159] Doubly activated olefins [173,174] and bromonaphthoquinone [175,176] are also likely to react by SET.…”

Section: ) Electron Spin Resonance (Esr) and Chemically Inducedmentioning

confidence: 99%

Wherefore Art Thou Copper? Structures and Reaction Mechanisms of Organocuprate Clusters in Organic Chemistry

Nakamura

Mori

2000

Angew. Chem. Int. Ed.

270

186

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Organocopper reagents provide the most general synthetic tools in organic chemistry for nucleophilic delivery of hard carbanions to electrophilic carbon centers. A number of structural and mechanistic studies have been reported and have led to a wide variety of mechanistic proposals, some of which might even be contradictory to others. With the recent advent of physical and theoretical methodologies, the accumulated knowledge on organocopper chemistry is being put together into a few major mechanistic principles. This review will summarize first the general structural features of organocopper compounds and the previous mechanistic arguments, and then describe the most recent mechanistic pictures obtained through high‐level quantum mechanical calculations for three typical organocuprate reactions, carbocupration, conjugate addition, and SN2 alkylation. The unified view on the nucleophilic reactivities of metal organocuprate clusters thus obtained has indicated that organocuprate chemistry represents an intricate example of molecular recognition and supramolecular chemistry, which chemists have long exploited without knowing it. Reasoning about the uniqueness of the copper atom among neighboring metal elements in the periodic table will be presented.

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“…Fluorenone ketyl radical has been detected in a cuprate reaction of fluorenone [20]. Doubly activated olefins [67][68][69] and bromonaphthoquinone [70] also probably react through SET.…”

Section: Single-electron Transfer Theoremmentioning

confidence: 99%

Mechanisms of Copper‐mediated Addition and Substitution Reactions

Mori¹,

Nakamura²

2002

Modern Organocopper Chemistry

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Acyclic stereocontrol via and electron-transfer process. Remarkable stereochemical difference between one- and two-electron events

Cited by 41 publications

References 2 publications

Diastereoselective protonation on a radical anion in the photoallylation and photoreduction of 1,1-dicyano-2-methyl-3-phenyl-1-butene by allyltrimethylsilane

Diastereoselective protonation on a radical anion in the photoallylation and photoreduction of 1,1-dicyano-2-methyl-3-phenyl-1-butene by allyltrimethylsilane

Wherefore Art Thou Copper? Structures and Reaction Mechanisms of Organocuprate Clusters in Organic Chemistry

Mechanisms of Copper‐mediated Addition and Substitution Reactions

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