Department of Chemistry, University of Pavia , Viale Taramelli 10, 27100 Pavia, Italy.
Chem Rev. 2018 Feb 28;118(4):2080-2248. doi: 10.1021/acs.chemrev.7b00322. Epub 2018 Feb 14.
This review is focused on the enantioselective synthesis of 3,4-dihydropyran derivatives, whose importance as chiral building blocks in the synthesis of bioactive molecules and natural products is well established. The review analyzes the different synthetic strategies by grouping them as a function of the atom numbers of the reagents involved. Starting from the classical [4 + 2] and [2 + 4] approaches, the [3 + 3], [5 + 1], and [6] strategies have been sequentially analyzed, and for each of them, the asymmetry induced by both chiral metal complexes and different kinds of organocatalysts has been examined. More than 400 papers have been reviewed, whose results have been described in the highest synthetic manner, in the attempt to emphasize the mechanism of the chirality transfer from the chiral messengers to the reaction products. This analysis allows the great flexibility of the diverse catalytic systems, the complementary of the results obtained from the different reaction pathways, and the very high level of control of the achievable molecular complexity to be evidenced.
这篇综述主要关注 3,4-二氢吡喃衍生物的对映选择性合成，这些衍生物作为生物活性分子和天然产物合成中的手性砌块具有重要意义。综述分析了不同的合成策略，根据涉及的试剂的原子数将它们分组。从经典的[4+2]和[2+4]方法开始，依次分析了[3+3]、[5+1]和[6]策略，对于每种策略，都考察了手性金属配合物和不同种类的有机催化剂诱导的不对称性。综述了超过 400 篇论文，以最高的合成方式描述了它们的结果，试图强调手性从手性试剂向反应产物传递的机制。这种分析证明了各种催化体系的巨大灵活性、不同反应途径获得的结果的互补性以及可实现的分子复杂性的高度控制水平。
