NIH Public AccessAuthor
PLOS A single | www.plosone.orgGlucocorticoids Regulate Metastatic Activity
NIH Public AccessAuthor ManuscriptJ Am Chem Soc. Author manuscript; out there in PMC 2014 June 26.Published in final edited form as: J Am Chem Soc. 2013 June 26; 135(25): 9252254. doi:10.1021/ja402569j.NIHPA Author Manuscript NIHPA Author Manuscript NIHPA Author ManuscriptCatalytic Enantioselective OnePot Aminoborylation of Aldehydes: A Approach for Construction of Nonracemic Amino BoronatesKai Hong and James P. Morken Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, MassachusettsAbstractWe report a tactic for the conversion of aldehydes to enantiomericallyenriched amino boronates via the intermediacy of in situgenerated silylimines. This transformation is brought about by Ptcatalyzed asymmetric addition of B2(pin)two across the imine double bond. An appealing function with the intermediate diboration adduct is that it can be acylated straight and delivers hassle-free access to crucial Nacyl amino boronic ester derivatives. Chiral amino boronic acids have located widespread use as pharmacologically active agents, most notably as protease inhibitors, and have appeared as motifs in clinically relevant therapeutics for the treatment of several myeloma.1,2 These structures have also located use as chiral intermediates in asymmetric synthesis thereby additional extending their significance in organic chemistry.3 As vital as Nacyl amino boronic acids are, you can find only two successful methods obtainable for their synthesis in an asymmetric fashion. Matteson has established a diastereoselective homologation of pinanediolderived boronic esters that is achieved by remedy with dichloromethyllithium; the item of this reaction is actually a chiral chloro boronic ester that may possibly undergo stereospecific substitution with amine nucleophiles delivering amino boronates (eq.Ethyl 5-bromo-1H-imidazole-2-carboxylate web 1, Scheme 1).four In a different method, Ellman has introduced a coppercatalyzed diastereoselective borylation of chiral sulfinylimines that furnishes amino boronic esters (eq. 2).five,6 We deemed that a catalytic enantioselective strategy that employs readily available substrates(1)Corresponding [email protected]. Supporting Data. Procedures, characterization and spectral data. This material is readily available no cost of charge by means of the web at http://pubs.acs.org. The authors declare no competing economic interest.Hong and MorkenPageNIHPA Author Manuscript NIHPA Author Manuscript NIHPA Author ManuscriptJ Am Chem Soc. Author manuscript; out there in PMC 2014 June 26.1936429-06-9 Chemscene (two)(3)and reagents may well streamline access to these critical motifs.PMID:23996047 Along these lines, we describe herein the direct conversion of aldehydes to amino boronic esters within a catalytic asymmetric style (eq. three). An important feature of this reaction strategy is that acylation with the amino boronic ester occurs right after CB bond formation such that diverse arrays of peptidic amino boronates might be accessed within a easy style. Recent research performed in our laboratory have demonstrated that chiral platinumphosphonite complexes can catalyze the enantioselective addition of B2(pin)2 across the systems discovered in isolated terminal alkenes and in conjugated dienes.7,eight It was viewed as that analogous enantioselective addition of B2(pin)two across imine double bonds would supply a straightforward route to amino boronic acid derivatives.9 As design criteria, we targeted a reaction where a) substrates are readily offered, and b) the reactio.
