2016年2月5日 · First of all, they can be used to perform conjugate addition reactions (“1,4-addition”) on alpha,-beta unsaturated ketones. In contrast, Grignard reagents tend to only add to the carbonyl carbon. Third, Gilman reagents will convert acid halides to ketones through nucleophilic acyl substitution.

In the reaction depicted below, [4] the Gilman reagent is a methylating reagent reacting with an alkyne in a conjugate addition, and the ester group forms a cyclic enone. Lithium dimethylcuprate exists as a dimer in diethyl ether forming an 8-membered ring.

1992年1月1日 · The 1H, 13C and 29Si NMR spectra were recorded for solutions of TMSI and [Me2CuLi]2, in a 1: 1 ratio, in ThF at -70C. On the addition of TMSI to the clear solution of [Me2CuLi]2 in ThF at -70C a rapid change takes place with the initial formation of a yellow precipitate which dissolves to a clear solution that slowly turns slightly red.

Mechanism of SN2 Alkylation Reactions of Lithium Organocuprate Clusters with Alkyl Halides and Epoxides. Solvent Effects, BF3 Effects, and Trans-Diaxial Epoxide Opening. Journal of the American Chemical Society 2000 , 122 (30) , 7294-7307.

2004年1月27日 · Anion Radical [2 + 2] Cycloaddition as a Mechanistic Probe: Stoichiometry- and Concentration-Dependent Partitioning of Electron-Transfer and Alkylation Pathways in the Reaction of the Gilman Reagent Me2CuLi·LiI with Bis(enones).

2013年6月18日 · Typical aldehydes and ketones form π complexes with Me2CuLi at low temperatures in tetrahydrofuran. They range in stability from fleeting intermediates at −100 °C to entities that persist up to −20...

2004年11月12日 · Complete partitioning of the Gilman alkylation and [2 + 2] cycloaddition pathways may be achieved by adjusting the loading of the Gilman reagent, the rate of addition of the Gilman reagent, and the concentration of the reaction mixture.

1997年1月1日 · The alkenylcopper adduct (1) from the conjugate addition of Me 2 CuLi · LiI (3) to methyl 4,4-dimethyl-2-pentynoate (2) forms a π-complex when exposed to an excess of the starting acetylene.

2022年5月5日 · 二甲基铜锂是有机合成中常用的一种甲基化试剂，可以和各种α,β-不饱和羰基化合物发生1,4-共轭加成反应、1,2-加成反应、炔烃的酮羰基化和碳-杂原子键的还原反应等。 此外，二甲基铜锂还可以和烷基、乙烯基、烯丙基类化合物发生取代反应。 二烷基铜锂可以和各种不饱和底物发生1,4-共轭加成 [3]，例如：烯酮、烯醇、烯酯、炔酮、炔酯以及 α,β-不饱和内酯、酰亚胺和磷酸酯等。 反应通常在非极性溶剂（例如：乙醚、甲苯、二氯甲烷、戊烷）中进行，极性溶 …

Alkylation of the enolate with isobutyl bromide will likely give substantial elimination. 3-Bromo-2-methylprop-1-ene will be more reactive and not undergo elimination. Reduce the double bond with Pd/C/H2. Alternatively, trap the enolate with isobutyraldehyde, …