20023-36-3Relevant articles and documents
Scalable and safe synthetic organic electroreduction inspired by Li-ion battery chemistry
Peters, Byron K.,Rodriguez, Kevin X.,Reisberg, Solomon H.,Beil, Sebastian B.,Kawamata, Yu,Baran, Phil S.,Hickey, David P.,Klunder, Kevin,Gorey, Timothy J.,Anderson, Scott L.,Minteer, Shelley D.,Collins, Michael,Starr, Jeremy,Chen, Longrui,Udyavara, Sagar,Neurock, Matthew
, p. 838 - 845 (2019/04/30)
Reductive electrosynthesis has faced long-standing challenges in applications to complex organic substrates at scale. Here, we show how decades of research in lithium-ion battery materials, electrolytes, and additives can serve as an inspiration for achieving practically scalable reductive electrosynthetic conditions for the Birch reduction. Specifically, we demonstrate that using a sacrificial anode material (magnesium or aluminum), combined with a cheap, nontoxic, and water-soluble proton source (dimethylurea), and an overcharge protectant inspired by battery technology [tris(pyrrolidino)phosphoramide] can allow for multigram-scale synthesis of pharmaceutically relevant building blocks. We show how these conditions have a very high level of functional-group tolerance relative to classical electrochemical and chemical dissolving-metal reductions. Finally, we demonstrate that the same electrochemical conditions can be applied to other dissolving metal-type reductive transformations, including McMurry couplings, reductive ketone deoxygenations, and epoxide openings.
SmI2/H2O/amine promoted reductive cleavage of benzyl-heteroatom bonds: optimization and mechanism
Ankner, Tobias,Hilmersson, G?ran
experimental part, p. 10856 - 10862 (2010/02/28)
The SmI2/H2O/pyrrolidine mediated cleavage of benzylic alcohols and benzyl groups was studied and found to be a viable alternative to the Birch reduction yielding the corresponding deoxygenated product in excellent yield. The reaction has been investigated by kinetic methods, and a mechanism involving a pre-complexation of the alcohol to SmI2 followed by an amine mediated electron transfer and subsequent bond cleavage and transfer of a second electron and proton to yield the toluene product has been proposed. The reaction is strongly inhibited at higher concentrations of water, indicating that it proceeds via an inner-sphere electron transfer from samarium(II) to the benzyl group, and excess of water prevents coordination of benzyl alcohol to samarium.
Synthesis Based on Cyclohexadienes. V. A New Approach to the Synthesis of A-Ring Aromatic Steroids: a Formal Total Synthesis of (+/-)-Estrone
Rao, G. S. R. Subba,Banerjee, D. K.,Devi, L. Uma,Sheriff, Uma
, p. 187 - 203 (2007/10/02)
A new strategy for the construction of A-ring aromatic steroids which resulted in the formal total synthesis of estrone is described.Thus reaction of the adduct (9), obtained from 1-methoxy-4-methylcyclohexa-1,4-diene and acrolein, with 3-(m-methoxyphenyl
