Allylmagnesation and Diallylation of Acetylenic Compounds Catalyzed by Manganese Salts

Okada, Kenji; Oshima, Koichiro; Utimoto, Kiitirô

doi:10.1021/ja960791y

Cited by 61 publications

(10 citation statements)

References 10 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…[56] The manganese-catalyst created an alkenyl Grignard reagent which could then react further with a range of electrophiles. Oshima and co-workers used allylmagnesium bromide and simple manganese salts to perform a range of transformations from alkyne starting materials 192 (Scheme 30).…”

Section: Carbometallationmentioning

confidence: 99%

“…Oshima and co-workers used allylmagnesium bromide and simple manganese salts to perform a range of transformations from alkyne starting materials 192 (Scheme 30). [56] The manganese-catalyst created an alkenyl Grignard reagent which could then react further with a range of electrophiles. For alkynes with a vinyl ether substituent 195, rearrangement to a diene product 196 was observed and proposed to proceed through a cyclic intermediate 198.…”

Section: Carbometallationmentioning

confidence: 99%

See 1 more Smart Citation

Recent Advances of Manganese Catalysis for Organic Synthesis

2016

View full text Add to dashboard Cite

Manganese is a non‐toxic, inexpensive and earth abundant metal, so is a perfect candidate for catalysis whether as a replacement for precious metals or in the search for novel reactivity. Despite this, manganese catalysis has not undergone the same development of other earth‐abundant metals (particularly iron and cobalt). This review details recent synthetic methodologies using manganese catalysts, including C–H activation, late stage fluorination, hydrosilylation and cross‐coupling.

show abstract

Section: Carbometallationmentioning

confidence: 99%

Section: Carbometallationmentioning

confidence: 99%

Recent Advances of Manganese Catalysis for Organic Synthesis

2016

View full text Add to dashboard Cite

show abstract

“…Oshima reported manganese-catalyzed regio- and stereoselective carbomagnesiation of homopropargyl ether 2d leading to the formation of the corresponding syn- addition product 2e (Scheme 9) [65]. The reaction of [2-(1-propynyl)phenyl]methanol ( 2f ) also proceeded in a syn fashion (Scheme 10) [66–68].…”

Section: Reviewmentioning

confidence: 99%

Recent advances in transition-metal-catalyzed intermolecular carbomagnesiation and carbozincation

Murakami¹,

Yorimitsu²

2013

Beilstein J. Org. Chem.

View full text Add to dashboard Cite

SummaryCarbomagnesiation and carbozincation reactions are efficient and direct routes to prepare complex and stereodefined organomagnesium and organozinc reagents. However, carbon–carbon unsaturated bonds are generally unreactive toward organomagnesium and organozinc reagents. Thus, transition metals were employed to accomplish the carbometalation involving wide varieties of substrates and reagents. Recent advances of transition-metal-catalyzed carbomagnesiation and carbozincation reactions are reviewed in this article. The contents are separated into five sections: carbomagnesiation and carbozincation of (1) alkynes bearing an electron-withdrawing group; (2) alkynes bearing a directing group; (3) strained cyclopropenes; (4) unactivated alkynes or alkenes; and (5) substrates that have two carbon–carbon unsaturated bonds (allenes, dienes, enynes, or diynes).

show abstract

“…The addition of Grignard reagents across carbon-carbon multiple bonds (carbomagnesiation) is a principal and important reaction in organic syntheses for the generation of Grignard reagents with the complicated structure of carbon skeletons. 1 It is known that methyl, aryl, allyl, and primaryalkyl Grignard reagents efficiently undergo carbomagnesiation and form diverse unsaturated hydrocarbons such as alkenes, alkynes, and dienes in the absence or presence of transition metal catalysts (Zr, 2 Ti, 3 Mn, 4 Fe, 5 Ni, 6 Cu). 7 However, branched alkyl Grignard reagents such as sec-and tert-alkyl Grignard reagents are generally poor substrates for such transformations, 8 particularly for non-activated unsaturated hydrocarbons having no heteroatom moieties.…”

mentioning

confidence: 99%