74962-99-5Relevant articles and documents
Bulky Cyclometalated Ruthenium Nitrates for Challenging Z-Selective Metathesis: Efficient One-Step Access to α-Oxygenated Z-Olefins from Acrylates and Allyl Alcohols
Gan, Quan,Grubbs, Robert H.,Ko, Jeong Hoon,Samkian, Adrian E.,Xu, Yan
supporting information, (2021/12/10)
α-Oxygenated Z-olefins are ubiquitous in biologically active molecules and serve as versatile handles for organic synthesis, but their syntheses are often tedious and less selective. Here we report the efficient Z-selective metathesis of various terminal
Stereoretentive Olefin Metathesis Made Easy: In Situ Generation of Highly Selective Ruthenium Catalysts from Commercial Starting Materials
Müller, Daniel S.,Curbet, Idriss,Raoul, Yann,Le N?tre, Jér?me,Baslé, Olivier,Mauduit, Marc
supporting information, p. 6822 - 6826 (2018/10/31)
The in situ preparation of highly stereoretentive ruthenium-based metathesis catalysts is reported. This approach completely avoids the isolation of intermediates and air-sensitive catalysts, thus allowing for the rapid access and evaluation of numerous dithiolate Ru catalysts. A procedure was established to perform cross-metathesis reactions without the use of a glovebox, and on a small scale even Schlenk techniques are not required. Consequently, the chemistry displayed in this report is available to every practicing organic chemist and presents a powerful approach for the identification of new stereoretentive catalysts.
High-value alcohols and higher-oxidation-state compounds by catalytic Z-selective cross-metathesis
Koh, Ming Joo,Khan, R. Kashif M.,Torker, Sebastian,Yu, Miao,Mikus, Malte S.,Hoveyda, Amir H.
, p. 181 - 186 (2015/03/30)
Olefin metathesis catalysts provide access to molecules that are indispensable to physicians and researchers in the life sciences. A persisting problem, however, is the dearth of chemical transformations that directly generate acyclic Z allylic alcohols, including products that contain a hindered neighbouring substituent or reactive functional units such as a phenol, an aldehyde, or a carboxylic acid. Here we present an electronically modified ruthenium-disulfide catalyst that is effective in generating such high-value compounds by cross-metathesis. The ruthenium complex is prepared from a commercially available precursor and an easily generated air-stable zinc catechothiolate. Transformations typically proceed with 5.0 mole per cent of the complex and an inexpensive reaction partner in 4-8 hours under ambient conditions; products are obtained in up to 80 per cent yield and 98:2 Z:E diastereoselectivity. The use of this catalyst is demonstrated in the synthesis of the naturally occurring anti-tumour agent neopeltolide and in a single-step stereoselective gram-scale conversion of a renewable feedstock (oleic acid) to an anti-fungal agent. In this conversion, the new catalyst promotes cross-metathesis more efficiently than the commonly used dichloro-ruthenium complexes, indicating that its utility may extend beyond Z-selective processes.
