Reginato G, Meffre P, Gaggini F
CNR ICCOM, Istituto di Chimica dei Composti Organo Metallici, Dipartimento di Chimica Organica U. Schiff, Università di Firenze, Polo Scientifico, Sesto Fiorentino, Italy.
Amino Acids. 2005 Aug;29(2):81-7. doi: 10.1007/s00726-005-0184-y. Epub 2005 Apr 11.
The ethynylglycine synthon, namely (R)-2,2-dimethyl-3-(tert-butoxycarbonyl)-4-ethynyl-oxazolidine, can be obtained through the synthetic elaboration of naturally occurring serine. This compound has been exploited as a helpful and versatile non-racemic building block to be used for the design and synthesis of biologically important compounds, mainly non-natural alpha-amino acids. Taking advantage of the terminal acetylene moiety several synthetic applications can be designed. Metalation followed by trapping with electrophiles or Cu/Pd catalysed coupling with aromatic halogenides are shown to deliver useful precursors of ethynylglycine derivatives. Additions of bimetallic reagents like stannyl- or silylcuprates are useful entries for the regio- and stereoselective functionalization of the lateral chain, aimed at the synthesis of modified vinylglycine precursors. An overview of our recent work in the field will be given, and the use of ethynylglycine synthon in the synthesis of non-racemic saturated and unsaturated non-natural amino acids will be briefly reviewed.
乙炔基甘氨酸合成子，即(R)-2,2-二甲基-3-(叔丁氧羰基)-4-乙炔基-恶唑烷，可以通过对天然存在的丝氨酸进行合成精制而得到。该化合物已被用作一种有用且通用的非外消旋结构单元，用于设计和合成具有生物学重要性的化合物，主要是非天然α-氨基酸。利用末端乙炔部分，可以设计出多种合成应用。金属化后用亲电试剂捕获或铜/钯催化与芳基卤化物偶联，可得到乙炔基甘氨酸衍生物的有用前体。添加双金属试剂如锡基或硅基铜酸盐，是侧链区域和立体选择性官能化的有用方法，旨在合成修饰的乙烯基甘氨酸前体。将概述我们近期在该领域的工作，并简要回顾乙炔基甘氨酸合成子在非外消旋饱和及不饱和非天然氨基酸合成中的应用。
