Development of Novel Chiral Synthons for 2-Amino Alcohols of Biological Interest.

1. Vesatile手性合成子：以2-exo-alkoxy-apocamphanecarboxylic acid衍生物为手性助剂，通过甲氧基溴化、甲氧基硒化和[4+2]环加成反应，将2-恶唑酮对映体选择性地功能化为反应中间体。该反应具有良好的非对映选择性，为制备对映体纯的2-氨基醇提供了简便的途径.具有生物学意义的2-氨基醇的合成：如上所述的二氢吡喃酮被有效地转化为生物活性氨基-羟基羧酸醇，例如光学纯形式的他汀及其类似物、3-氨基-2-羟基-4-苯基丁酸（bestatin的组分）和3-氨基-2-羟基-5-甲基己酸（amastatin的组分）以及二氢鞘氨醇。新手性化合物：合成了具有双环[2.2.2]辛烷环结构的手性2-恶唑烷酮（DHAOx和DMAOx），并成功地用作Diels-Alder反应、烷基化反应、Aldol反应和Michael反应中的高效助剂。通过上述DHAOx和DMAOx的开环容易地获得的2-氨基醇的两种对映异构体在醛与二烷基锌的对映选择性烷基化中充当优异且独特的催化剂。高反应性缩合试剂：由2-恶唑酮活化的硫代磷酰基衍生物被开发为用于合成酰胺（包括肽和β-内酰胺）、酯和硫酯的强大且稳定的缩合试剂。

1. Vesatile Chiral Synthons : Using the 2-exo-alkoxy-apocamphanecarboxylic acid derivatives as chiral auxiliaries, 2-oxazolone was enantioselectively functionalized to the reactive intermediates (synthons) by means of methoxybromination, methoxyselenylation and [4+2]cycloaddition reactions. Stepwise and stereospecific conversions of the synthons, thus obtained with excellent diastereoselectivity, provided facile routes for the preparation of enantiomerically pure 2-amino alcohols.2. Syntheses of 2-Amino Alcohols of Biological Interest : The synthons, described as above, were effectively converted to bioactive amino-hydroxycarboxylic acids alcohols such as statine and its analogues, 3-amino-2-hydroxy-4-phenylbutanoic acid (component of bestatine), and 3-amino-2-hydroxy-5-methylhexanoic acid (component of amastatin), in optically pure forms as well as dihydrosphingosine.3. New Chiral Auxiliaries : Chiral 2-oxazolidinones featured by bicyclo [2.2.2] octane ring system (DHAOx and DMAOx) were synthesized and successfully utilized as highly efficient auxiliaries in the Diels-Alder reactions, alkylations, aldol reactions and the Michael reactoins. Both enentiomers of the 2-amino alcohols, readily obtained by ring opening of the above DHAOx and DMAOx, served as excellent and unique catalysts in enantioselective alkylations of aldehydes with dialkylzinc.4. Highly Reactive Condensing Reagents : Thiophosphoryl derivatives activated by 2-oxazolone were developed as powerful and stable condensing reagents for the synthesis of amides including peptides and beta-lactams, esters and thioesters.