The stereochemistry of the coupling reactions of oxygen-substituted bromides 8-10 with isobutyraldehyde, benzaldehyde, and cyclohexanecarboxaldehyde in water is described. The examples involving the O-silylated derivatives 8 exhibit moderate anti stereoselectivity. In contrast, rather high (most often in excess of 80:20) syn diastereofacial bias is observed when hydroxy bromides 10 are involved. Consequently, stereocontrolled 1,4-asymmetric induction under aqueous conditions can be realized in either direction on demand. These results are considered to reflect the fact that the siloxy systems enter into C-C bond formation via conventional Felkin-Anh transition state arrangements. The crossover observed for the unprotected analogues is believed to be a consequence of the preferred adoption of chelated transition states, these interactions likely being fundamental to aqueous organometallic chemistry.S0022-3263(97)01553-3 CCC: $15.00
Based on a technology that won a Presidential Green Chemistry Challenge Award, this experiment involves the thermal polymerization of aspartic acid and subsequent hydrolysis to give sodium poly(aspartate). The procedure is suitable for introducing students to the important topic of polymers and for illustrating several of the principles of green chemistry.
The preparation and indium-promoted aldehyde addition reactions of a series of 3-substituted 3-oxy-1-bromo-2-methylidenepropanes under aqueous conditions are described. The (tert-butyldimethylsilyl)oxy derivatives 4a-d are the most diastereoselective of this group of reagents, giving rise to levels of syn-1,4-asymmetric induction in the range of 87-99%. Interestingly, syn stereoselectivity is eroded and reactions proceed more rapidly when the steric bulk of the oxygen substituent is reduced as in the hydroxy and methoxy derivatives. This dropoff in pi-facial differentiation with kinetic acceleration is attributed to the operation of chelation effects during oxidative addition of the metal into the carbon-bromine bond, but not during the coupling stage. Once the aldehyde enters into the coordination sphere of the indium, internal chelation to the proximal oxygen is disrupted and conformational restrictions are released. These effects, in combination with the absence of a powerful steric control element in the latter examples, permit competitive passage via syn and anti transition states.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.