Our Communication did not emphasize important safety considerations in the reported reactions.Buchwald and co-workers previously studied the Ti-catalyzed reduction of amides to amines or enamines. 1 Additionally, in 1992, Berk and Buchwald reported the combination of 5 mol % Ti(O-i-Pr) 4 with 2.5-3.0 equiv of (EtO) 3 SiH for the reduction of esters to silyl ethers at 40-55°C. 2 An attempt to use this procedure for the reduction of a methyl ester (90 mmol) with triethoxysilane (313 mmol) resulted in the formation of an extremely pyrophoric gas (possibly SiH 4 ), leading to several fires and an explosion. 3 During our studies on the reduction of amides, we used triethoxysilane without incident, although the Material Safety Data Sheet indicates that this chemical is a corrosive and flammable liquid. Due to the previously reported hazards, we advise that methyldiethoxysilane be used instead of triethoxysilane for the large-scale (>1 g) reduction of amides. As shown in the Supporting Information of our Communication, methyldiethoxysilane and other organosilanes can also be used for the reduction of amides at slightly higher temperature, e.g. 60°C. We thank Professor Buchwald for pointing out these latent safety problems with triethoxysilane.
Literature Cited(1) Kreutzer, K. A.Page 5907. The crystal structure reported was not that of (FI 2 Ni 2 PMe 3 ) · PMe 3 but that of a decomposition product. The structure is now clarified by Delferro et al. 1
Literature Cited(1) Delferro, M.; Weberski, M. P., Jr.; Rodriguez, B. A.; Marks, T. J.Acta Crystallogr. 2010, E66, m258.We regret the omission of a prior publication describing the relative affinities of poly [(9,9-bis(6′-N,N,N-trimethylammonium)hexyl)fluorene-alt-1,4-phenylene]bromide (PFP-Br) and single-and double-stranded DNA that has recently come to our attention. Some years prior to our work, Liu and Bazan 1 demonstrated improved fluorescence energy transfer from PFP, Br to acceptor-labeled single-stranded DNA relative to transfer to acceptor-labeled double-stranded DNA. We hereby acknowledge this precedent. Literature Cited (1) Liu, B.; Bazan, G. C.
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.