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. 2013:9:278-302.
doi: 10.3762/bjoc.9.34. Epub 2013 Feb 11.

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

Kei Murakami  1 , Hideki Yorimitsu
Affiliations

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

Kei Murakami et al. Beilstein J Org Chem. 2013.

Abstract

Carbomagnesiation 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).

Keywords: alkene; alkyne; carbomagnesiation; carbometalation; carbozincation; transition metal.

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Figures

Scheme 1
Scheme 1
Variation of substrates for carbomagnesiation and carbozincation in this article.
Scheme 2
Scheme 2
Copper-catalyzed arylmagnesiation and allylmagnesiation of alkynyl sulfone.
Scheme 3
Scheme 3
Copper-catalyzed four-component reaction of alkynyl sulfoxide with alkylzinc reagent, diiodomethane, and benzaldehyde.
Scheme 4
Scheme 4
Rhodium-catalyzed reaction of aryl alkynyl ketones with arylzinc reagents.
Scheme 5
Scheme 5
Allylmagnesiation of propargyl alcohol, which provides the anti-addition product.
Scheme 6
Scheme 6
Negishi’s total synthesis of (Z)-γ-bisabolene by allylmagnesiation.
Scheme 7
Scheme 7
Iron-catalyzed syn-carbomagnesiation of propargylic or homopropargylic alcohol.
Scheme 8
Scheme 8
Mechanism of iron-catalyzed carbomagnesiation.
Scheme 9
Scheme 9
Regio- and stereoselective manganese-catalyzed allylmagnesiation.
Scheme 10
Scheme 10
Vinylation and alkylation of arylacetylene-bearing hydroxy group.
Scheme 11
Scheme 11
Arylmagnesiation of (2-pyridyl)silyl-substituted alkynes.
Scheme 12
Scheme 12
Synthesis of tamoxifen from 2g.
Scheme 13
Scheme 13
Controlling regioselectivity of carbocupration by attaching directing groups.
Scheme 14
Scheme 14
Rhodium-catalyzed carbozincation of ynamides.
Scheme 15
Scheme 15
Synthesis of 4-pentenenitriles through carbometalation followed by aza-Claisen rearrangement.
Scheme 16
Scheme 16
Uncatalyzed carbomagnesiation of cyclopropenes.
Scheme 17
Scheme 17
Iron-catalyzed carbometalation of cyclopropenes.
Scheme 18
Scheme 18
Enantioselective carbozincation of cyclopropenes.
Scheme 19
Scheme 19
Copper-catalyzed facially selective carbomagnesiation.
Scheme 20
Scheme 20
Arylmagnesiation of cyclopropenes.
Scheme 21
Scheme 21
Enantioselective methylmagnesiation of cyclopropenes without catalyst.
Scheme 22
Scheme 22
Copper-catalyzed carbozincation.
Scheme 23
Scheme 23
Enantioselective ethylzincation of cyclopropenes.
Scheme 24
Scheme 24
Nickel-catalyzed ring-opening aryl- and alkenylmagnesiation of a methylenecyclopropane.
Scheme 25
Scheme 25
Reaction mechanism.
Scheme 26
Scheme 26
Nickel-catalyzed carbomagnesiation of arylacetylene and dialkylacetylene.
Scheme 27
Scheme 27
Nickel-catalyzed carbozincation of arylacetylenes and its application to the synthesis of tamoxifen.
Scheme 28
Scheme 28
Bristol-Myers Squibb’s nickel-catalyzed phenylzincation.
Scheme 29
Scheme 29
Iron/NHC-catalyzed arylmagnesiation of aryl(alkyl)acetylene.
Scheme 30
Scheme 30
Iron/copper-cocatalyzed alkylmagnesiation of aryl(alkyl)acetylenes.
Scheme 31
Scheme 31
Iron-catalyzed hydrometalation.
Scheme 32
Scheme 32
Iron/copper-cocatalyzed arylmagnesiation of dialkylacetylenes.
Scheme 33
Scheme 33
Chromium-catalyzed arylmagnesiation of alkynes.
Scheme 34
Scheme 34
Cobalt-catalyzed arylzincation of alkynes.
Scheme 35
Scheme 35
Cobalt-catalyzed formation of arylzinc reagents and subsequent arylzincation of alkynes.
Scheme 36
Scheme 36
Cobalt-catalyzed benzylzincation of dialkylacetylene and aryl(alkyl)acetylenes.
Scheme 37
Scheme 37
Synthesis of estrogen receptor antagonist.
Scheme 38
Scheme 38
Cobalt-catalyzed allylzincation of aryl-substituted alkynes.
Scheme 39
Scheme 39
Silver-catalyzed alkylmagnesiation of terminal alkyne.
Scheme 40
Scheme 40
Proposed mechanism of silver-catalyzed alkylmagnesiation.
Scheme 41
Scheme 41
Zirconium-catalyzed ethylzincation of terminal alkenes.
Scheme 42
Scheme 42
Zirconium-catalyzed alkylmagnesiation.
Scheme 43
Scheme 43
Titanium-catalyzed carbomagnesiation.
Scheme 44
Scheme 44
Three-component coupling reaction.
Scheme 45
Scheme 45
Iron-catalyzed arylzincation reaction of oxabicyclic alkenes.
Scheme 46
Scheme 46
Reaction of allenyl ketones with organomagnesium reagent.
Scheme 47
Scheme 47
Regio- and stereoselective reaction of a 2,3-allenoate.
Scheme 48
Scheme 48
Three-component coupling reaction of 1,2-allenoate, organozinc reagent, and ketone.
Scheme 49
Scheme 49
Proposed mechanism for a rhodium-catalyzed arylzincation of allenes.
Scheme 50
Scheme 50
Synthesis of skipped polyenes by iterative arylzincation/allenylation reaction.
Scheme 51
Scheme 51
Synthesis of 1,4-diorganomagnesium compound from 1,2-dienes.
Scheme 52
Scheme 52
Synthesis of tricyclic compounds.
Scheme 53
Scheme 53
Manganese-catalyzed allylmagnesiation of allenes.
Scheme 54
Scheme 54
Copper-catalyzed alkylmagnesiation of 1,3-dienes and 1,3-enynes.
Scheme 55
Scheme 55
Chromium-catalyzed methallylmagnesiation of 1,6-diynes.
Scheme 56
Scheme 56
Chromium-catalyzed allylmagnesiation of 1,6-enynes.
Scheme 57
Scheme 57
Proposed mechanism of the chromium-catalyzed methallylmagnesiation.
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