Carbometalation
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Carbometalation is an organometallic reaction involving the nucleophilic addition to alkenes and alkynes of a diverse range of organometallic reagents such as organolithium compounds, organocopper compounds and Grignard reagents according to the following general alkyne scheme:
The addition can yield the cis or trans isomer and with unsymmetrical alkynes the organometallic compound can add in two different way thus control of regioselectivity is important.
In a follow-up step the sensitive metalalkenyl group is replaced by an electrophile E+.
[edit] Scope
In one study methylphenylacetylene is reacted with phenylmagnesium bromide to a vinyl magnesium bromide which is quenched with water [1] [2] :
Another demonstration of this reaction type is an alternative route to tamoxifen starting from diphenylacetylene and ethyllithium [3]:
The capturing electrophile here is triisopropyl borate forming the boronic acid R-B(OH)2. The second step completing tamoxifen is a Suzuki reaction.
[edit] Silylmetalation
This reaction type can be extended to compounds of silicon bonded to a suitable metal in so-called silylmetalation as an extention to hydrosilylation. In one study [4]a zinc ate complex is formed from dimethylphenylsilyllithium, 2,2'-biphenol, zinc chloride and the Grignard reagent of tert-butylchloride which is capable of silylmetalation to styrene with 100% regioselectivity:
The intermediate complex can be captured with many electrophiles such as propargyl bromide (pictured, forming the allene), benzoyl chloride and allyl bromide.
[edit] References
- ^ Arylmagnesiation of Alkynes Catalyzed Cooperatively by Iron and Copper Complexes Eiji Shirakawa, Takafumi Yamagami, Takahiro Kimura, Shigeru Yamaguchi, and Tamio Hayashi J. Am. Chem. Soc.; 2005; 127(49) pp 17164 - 17165; (Communication) DOI:10.1021/ja0542136
- ^ In this reaction the Grignard reagent together with iron acetylacetonate and tributylphosphine first form an ill-defined aryliron intermediate and then by reaction with copper(I) chloride an intermediate cuprate
- ^ Carbolithiation of Diphenylacetylene as a Stereoselective Route to (Z)-Tamoxifen and Related Tetrasubstituted Olefins Neola F. McKinley and Donal F. O'Shea J. Org. Chem.; 2006; 71(25) pp 9552 - 9555; (Note) DOI:10.1021/jo061949s
- ^ Regio- and Chemoselective Silylmetalation of Functionalized Terminal Alkenes Shinji Nakamura and Masanobu Uchiyama J. Am. Chem. Soc.; 2007; 129(1) pp 28 - 29; (Communication) DOI:10.1021/ja066864n
Principles: Electron counting, 18-Electron rule, Isolobal principle, π backbonding
Reactions: Oxidative addition, Reductive elimination, Beta-hydride elimination, Transmetalation, Carbometalation
Types of compounds: Gilman reagent, Grignard reagents, Cyclopentadienyl complexes, Metallocenes, Sandwich compound, Transition metal carbene complexes
Applications: Monsanto process, Ziegler-Natta catalyst, Olefin metathesis
Related branches of chemistry: Organic chemistry - Inorganic chemistry - Bioinorganic chemistry
