An Unusual Rearrangement of N,N-Dibenzyl-2-aminopropanal to N,N-Dibenzyl-1-aminopropanone.

Synthesis and Diastereoselective Reactions of N,N-Dibenzylamino Aldehydes and Related Compounds

“…Chromatographic purification is not necessary and, in fact, should be avoided because of partial racemization . Upon storing the aldehydes for long periods of time (months), partial rearrangement to achiral α -amino ketones may occur, − a process that is accelerated by bases or acids. , Keeping these precautions in mind, handling the aldehydes is straightforward, even on an industrial scale. ,− If long-term storage and/or shipping is necessary, stabilization can be achieved by transformation into the sodium bisulfite addition product as described in a patent …”

“…Chromatographic purification is not necessary and, in fact, should be avoided because of partial racemization. 26 Upon storing the aldehydes for long periods of time (months), partial rearrangement to achiral R-amino ketones may occur, [32][33][34] a process that is accelerated by bases or acids. 32,33 Keeping these precautions in mind, handling the aldehydes is straightforward, even on an industrial scale.…”

Conformational Control in Stereoselective Chemical Reactions: From Amino Acids to Iminosugars

“…Although pleased with the diastereoselectivity, we were concerned with the fact that the chiral starting material was an aldehyde reacting with a basic nucleophile, thus making the original stereocenter vulnerable to epimerization. [5][6][7]…”

Diastereoselective synthesis of vicinal amino alcohols

“…In some cases rearrangements occur and in most cases extensive, even total, racemization as per Whiting et al's report. 7 The third class of amino aldehyde that appear in the literature with some frequency are the singly protected amino aldehydes. The protecting group must be chosen with care, as the high nucleophilicity of the amino moiety must be kept in check.…”

“…The hormones epinephrine (4) and norepinephrine (5) are amino alcohols as well. Many others can be encountered beyond the safety of the human body ranging from small hydroxylated alkaloids like the glycosidase inhibitor nojirimycin (6) and the antimalarial agent febrifugine (7) to depsipeptides like the anticancer agent hapalosin (8) to amino sugars like antibiotic neomycin (9). Due to the diverse biological activities the amino alcohol moiety has been incorporated into pharmaceuticals as well.…”