Method for synthesizing high-regioselectivity alpha-alkenyl stannane through hydrogenation of terminal alkyne Martensite tin

Abstract

The method comprises the following steps: under the protection of inert gas, reacting an alkyne compound as shown in a formula I and trisubstituted tin hydride as shown in a formula II in an organic solvent by taking cobalt salt CoY2 as a metal salt catalyst and taking amide oxazoline as a ligand to obtain the alpha-alkenyl stannane with high regioselectivity. The alpha-alkenyl stannane compound as shown in a formula III is prepared; the reaction formula is shown in the specification. According to the method, the cheap metal cobalt is used as the central metal, the asymmetric tridentate nitrogen-containing ligand quinoline amide gem-dimethyl oxazoline is used as the ligand, the ligand is simple and easy to obtain, a catalyst does not need to be prepared in advance, and the metal salt and the ligand are subjected to in-situ complexation. The ligand and the metal salt involved in the reaction are not sensitive to water and oxygen, so that the practicability of the catalytic system is improved. The method disclosed by the invention is mild in reaction condition, simple and convenient to operate, high in atom economy and relatively excellent in yield (44-gt; the regioselectivity is high (greater than or equal to 97: 3), and the functional group compatibility is excellent.

Description

technical field [0001] This paper relates to a method for the synthesis of α-alkenylstannanes with high regioselectivity by hydrogenation of terminal alkyne martensitane. Background technique [0002] Organotin compounds have a wide range of applications in organic synthesis and pharmaceutical production [(a) Pereyr, M.; Quintard, J.-P.; Rahm, A. Tin in Organic Synthesis (Butterworths: London), 1987. (b) Yamamoto, H. Main Group Metals in Organic Synthesis. Oshima, K., eds. (Wiley-VCH: Weinheim), 2004, Vols. 1 and 2.], especially in the coupling reaction of carbon-carbon bonds is of great significance, Namely Stille coupling reaction [(a) Milstein, D.; Stille, J.K.J.Am.Chem.Soc. 1978, 100, 3636-3638. (b) Stille, J.K.Angew.Chem., Int. 524.]. Alkynes are simple and readily available bulk chemicals, which can be synthesized industrially by acetylene gas and halide under the action of sodium amide, and can also be synthesized by some name reactions such as Corey-Fuchs reaction,...

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Problems solved by technology

Among them, the Cu-Fe bimetallic catalyst can realize the Markov tin hydrogen reaction of alkyl alkynes with high regioselectivity, but for aryl alkyne substrates, due to the influence of steric effect, only anti-Martensitic hydrogen reactions can be obtained. selective product

[Cheng, L.J.; Mankad, N.P.J.Am.Chem.Soc.2019, 141, 3710-3716.] In 2021, Wang Wenguang et al. developed a semiferrocene phosphine oxide or phosphine nitrogen catalyst for the tin hydrogenation of alkynes, although the reaction Mild and high regioselectivity, but the regioselectivity of the reaction is reduced for electron-withdrawing aryl alkyne substrates

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