Grubbs Cross-Metathesis Pathway for a Scalable Synthesis of γ-Keto-α,β-unsaturated Esters
نویسندگان
چکیده
A direct and scalable route to γ-keto-α,β-unsaturated esters, useful intermediates in medicinal chemistry and natural products synthesis, is reported. The key step involves the use of Grubbs' second-generation olefin metathesis catalyst for cross-metathesis of alkyl acrylates and 2° allylic alcohols. The metathesis step is followed by oxidation to give the desired products in high yield on scales of up to 25 g.
منابع مشابه
Olefin cross-metathesis, a mild, modular approach to functionalized cellulose esters†
Olefin cross-metathesis has been demonstrated to be a modular pathway for synthesis of a series of functionalized cellulose esters. As a proof of concept, cellulose acetate was acylated with two terminally olefinic acid chlorides, pent-4-enoyl chloride and undec-10-enoyl chloride, providing olefin-terminated cellulose esters with different side-chain lengths. These ω-unsaturated cellulose ester...
متن کاملThe non-metathetic role of Grubbs' carbene complexes: from hydrogen-free reduction of α,β-unsaturated alkenes to solid-supported sequential cross-metathesis/reduction.
An efficient and high-yielding "hydrogen-free" reduction of α,β-unsaturated alkenes was carried out employing Grubbs' catalyst in a non-metathetic role and Et(3)SiH. Conditions were optimized under microwave irradiation. Application to the solid-phase organic synthesis allows a facile construction of sp(3)-sp(3) carbon bonds through a sequential cross metathesis/olefin reduction.
متن کاملRuthenium-catalysed Z-selective cross metathesis of allylic-substituted olefins† †Electronic supplementary information (ESI) available: Experimental procedures and spectroscopic data for all new compounds. See DOI: 10.1039/c3sc52806e Click here for additional data file.
The Z-selective cross metathesis of allylic-substituted olefins is explored with recently developed ruthenium-based metathesis catalysts. The reaction proceeds with excellent stereoselectivity for the Z-isomer (typically >95%) and yields of up to 88% for a variety of allylic substituents. This includes the first synthesis of Z-α,β-unsaturated acetals by cross metathesis and their elaboration to...
متن کاملCopper-catalyzed cascade reactions of α,β-unsaturated esters with keto esters
A copper-catalyzed cascade reaction of α,β-unsaturated esters with keto esters is reported. It features a copper-catalyzed reductive aldolization followed by a lactonization. This method provides a facile approach to prepare γ-carboxymethyl-γ-lactones and δ-carboxymethyl-δ-lactones under mild reaction conditions.
متن کاملMicrosoft Word - Synthesis of porphyryl
Porphyrins with (un)saturated side–chains containing boron residues were developed as synthons for porphyrin functionalization. Porphyrins with mono and bis-substituted unsaturated boronyl residues were prepared in good yields (52–66 %) using a cross–metathesis approach in the presence of Grubbs I-generation catalysts. In all cases complete E–stereoselectivity (100 %) was observed. Furthermore,...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
عنوان ژورنال:
دوره 79 شماره
صفحات -
تاریخ انتشار 2014