Direct Mono-N-methylation of Solid-Supported Amino Acids: A Useful Application of the Matteson Rearrangement of α-Aminoalkylboronic Esters

Organic Letters

Volumn 3, Issue 10, 2001, Pages 1487-1490

  Laplante, Carmen ^a   Hall, Dennis G ^a  

^a UNIVERSITY OF ALBERTA   (Canada)

Author keywords

[No Author keywords available]

Indexed keywords

AMINO ACID; PLANT RESIN;

ARTICLE; CHEMISTRY; COMBINATORIAL CHEMISTRY; METHODOLOGY; METHYLATION; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; SYNTHESIS;

AMINO ACIDS; COMBINATORIAL CHEMISTRY TECHNIQUES; MAGNETIC RESONANCE SPECTROSCOPY; METHYLATION; RESINS, PLANT;

EID: 0035902222     PISSN: 15237060     EISSN: None     Source Type: Journal    
DOI: 10.1021/ol015803l     Document Type: Article

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31. It may be possible that an adventitious nucleophile such as traces of water, or perhaps the chloride counteranion, could cleave the amino-boronate B and lead to C prior to rinsing away excess electrophile (Figure 1).
32. N-Oxide formation was observed only in trials involving larger amounts of hydrogen peroxide for longer reaction times.
33. It also appears unlikely that hydrolysis of the ester linker by peroxide anion could play a role. The high yields of N-methylated amino acids from highly overalkylated resins did not correlate with the possibility of a repair mechanism involving selective hydrolysis.
34. Presumably, proton transfer from the hydrochloride salt of initial intermediate A by the base may be rate-limiting.
35. 2O (85:10:5).
36. Common minor impurities often originate from the starting resin (e.g., benzoic acid from capping of unfunctionalized sites, concomitant cleavage of small amounts of the PHB or HMPB-BHA linkers).
37. PHB: p-hydroxybenzyl. HMPB-BHA: 4-hydroxymethyl-3-methoxyphenoxybutyric acid benzhydrylamide, or SASRIN.
38. Highly functionalized amino acids with nucleophilic or oxidazable centers may not be suitable as substrates. For instance, methionine was found not to be tolerant of these N-methylation conditions.