三（三甲基硅基）硅基调控的醛交叉羟醛串联反应
Tris(trimethylsilyl)silyl-governed aldehyde cross-aldol cascade reaction.
作者信息
Boxer Matthew B, Yamamoto Hisashi
机构信息
Department of Chemistry, The University of Chicago, 5735 South Ellis Avenue, Chicago, IL 60637, USA.
出版信息
J Am Chem Soc. 2006 Jan 11;128(1):48-9. doi: 10.1021/ja054725k.
The use of the tris(trimethylsilyl)silyl (TTMSS) group in aldehyde-derived silyl enol ethers affords aldehyde cross-aldol products with high yields and allows for unprecedented reactivity. The reaction is catalyzed by 0.05 mol % of HNTf2, and can easily be managed to give beta,delta-bis-, beta,delta,gamma-tris-, and beta,delta,zeta-tris-hydroxy-aldehydes with extremely high selectivity by simple stoichiometric control. High diastereoselectivity is obtained in all cases, and the use of chiral aldehydes affords Felkin products when there are nonchelating substituents, chelation products when there is a chelating sbustituent, and syn products when there is beta-substitution. HNTf2 is proposed to be an initiator, and highly Lewis acidic TTMSSNTf2 is the true catalyst.
在醛衍生的硅基烯醇醚中使用三（三甲基硅基）硅基（TTMSS）基团可高产率地得到醛交叉羟醛缩合产物，并具有前所未有的反应活性。该反应由0.05 mol%的HNTf2催化，通过简单的化学计量控制，能够轻松地以极高的选择性得到β,δ-双羟基、β,δ,γ-三羟基和β,δ,ζ-三羟基醛。在所有情况下均获得了高非对映选择性，当存在非螯合取代基时，使用手性醛可得到费尔金产物；当存在螯合取代基时，得到螯合产物；当存在β-取代时，得到顺式产物。有人提出HNTf2是引发剂，而具有高路易斯酸性的TTMSSNTf2是真正的催化剂。
Zotero 插件