87482-75-5Relevant articles and documents
Ruthenium-Catalyzed α-Alkylation of Ketones Using Secondary Alcohols to β-Disubstituted Ketones
Thiyagarajan, Subramanian,Vijaya Sankar, Raman,Gunanathan, Chidambaram
supporting information, p. 7879 - 7884 (2020/11/02)
An assortment of aromatic ketones was successfully functionalized with a variety of unactivated secondary alcohols that serve as alkylating agents, providing β-disubstituted ketone products in good to excellent yields. Remarkably, challenging substrates such as simple acetophenone derivatives are effectively alkylated under this ruthenium catalysis. The substituted cyclohexanol compounds displayed product-induced diastereoselectivity. Mechanistic studies indicate the involvement of the hydrogen-borrowing pathway in these alkylation reactions. Notably, this selective and catalytic C-C bond-forming reaction requires only a minimal load of catalyst and base and produces H2O as the only byproduct, making this protocol attractive and environmentally benign.
Ruthenium-Catalyzed Direct Cross-Coupling of Secondary Alcohols to β-Disubstituted Ketones
Gunanathan, Chidambaram,Thiyagarajan, Subramanian
, p. 2027 - 2034 (2019/11/05)
The β-disubstituted ketone functionality is prevalent in biologically active compounds and in pharmaceuticals. A ruthenium-catalyzed direct synthesis of β-disubstituted ketones by cross-coupling of two different secondary alcohols is reported. This new protocol was applied to the synthesis of variety of β-disubstituted ketones from various cyclic, acyclic, symmetrical, and unsymmetrical secondary alcohols. An amine-amide metal-ligand cooperation in a Ru catalyst facilitates the activation and formation of covalent bonds in selective sequences to provide the products. Kinetic and deuterium-labeling experiments suggested that aliphatic alcohols oxidize faster than benzylic secondary alcohols. A plausible mechanism is proposed on the basis of mechanistic and kinetic studies. Water and H 2 are the only byproducts from this selective cross-coupling of secondary alcohols. 1 Introduction 2 Catalytic Self-or Cross-Coupling of Alcohols and Selectivity Challenges 3 Recent Developments in the Synthesis of β-Disubstituted Ketones 4 Scope of Ruthenium-Catalyzed Cross-Couplings of Secondary Alcohols 5 Mechanistic Studies and Proposed Mechanism 6 Conclusion.
Peroxide promoted tunable decarboxylative alkylation of cinnamic acids to form alkenes or ketones under metal-free conditions
Ji, Jing,Liu, Ping,Sun, Peipei
supporting information, p. 7546 - 7549 (2015/05/04)
A tunable decarboxylative alkylation of cinnamic acids with alkanes was developed to form alkenes or ketones under transition metal-free conditions. In the presence of DTBP or DTBP/TBHP, the reaction gave alkenes and ketones respectively via a radical mechanism in moderate to good yields. This journal is
