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PLOS One | www.plosone.orgGlucocorticoids Regulate Metastatic Activity
NIH Public AccessAuthor ManuscriptJ Am Chem Soc. Author manuscript; obtainable in PMC 2014 June 26.Published in final edited type as: J Am Chem Soc. 2013 June 26; 135(25): 9252254. doi:ten.1021/ja402569j.NIHPA Author Manuscript NIHPA Author Manuscript NIHPA Author ManuscriptCatalytic Enantioselective OnePot Aminoborylation of Aldehydes: A Approach for Building of Nonracemic Amino BoronatesKai Hong and James P. Morken Division 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 in the intermediate diboration adduct is the fact that it could be acylated directly and delivers easy access to important Nacyl amino boronic ester derivatives. Chiral amino boronic acids have found widespread use as pharmacologically active agents, most notably as protease inhibitors, and have appeared as motifs in clinically relevant therapeutics for the remedy of a number of myeloma.1,two These structures have also found use as chiral intermediates in asymmetric synthesis thereby additional extending their importance in organic chemistry.3 As important as Nacyl amino boronic acids are, there are actually only two successful techniques obtainable for their synthesis in an asymmetric style. Matteson has established a diastereoselective homologation of pinanediolderived boronic esters that is certainly accomplished by remedy with dichloromethyllithium; the item of this reaction is really a chiral chloro boronic ester that could undergo stereospecific substitution with amine nucleophiles giving amino boronates (eq.Price of 612501-45-8 1, Scheme 1).4-(Tert-butyl)picolinic acid Price 4 In a different strategy, Ellman has introduced a coppercatalyzed diastereoselective borylation of chiral sulfinylimines that furnishes amino boronic esters (eq. 2).5,6 We deemed that a catalytic enantioselective method that employs readily available substrates(1)Corresponding [email protected]. Supporting Facts. Procedures, characterization and spectral information. This material is readily available cost-free of charge by means of the online world at http://pubs.acs.org. The authors declare no competing monetary interest.Hong and MorkenPageNIHPA Author Manuscript NIHPA Author Manuscript NIHPA Author ManuscriptJ Am Chem Soc. Author manuscript; readily available in PMC 2014 June 26.(two)(three)and reagents may perhaps streamline access to these vital motifs. Along these lines, we describe herein the direct conversion of aldehydes to amino boronic esters in a catalytic asymmetric style (eq.PMID:33480262 3). A vital function of this reaction strategy is the fact that acylation with the amino boronic ester occurs soon after CB bond formation such that diverse arrays of peptidic amino boronates may be accessed within a basic fashion. Current studies performed in our laboratory have demonstrated that chiral platinumphosphonite complexes can catalyze the enantioselective addition of B2(pin)2 across the systems located in isolated terminal alkenes and in conjugated dienes.7,8 It was regarded 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 and style criteria, we targeted a reaction where a) substrates are readily out there, and b) the reactio.
