"Super silyl" group for diastereoselective sequential reactions: Access to complex chiral architecture in one pot
"Super silyl" group for diastereoselective sequential reactions: Access to complex chiral architecture in one pot
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DOI：
10.1021/ja0693542
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发表时间：
2007-03-14
影响因子：
15
通讯作者：
Yamamoto, Hisashi
中科院分区：
文献类型：
--
作者：
Boxer, Matthew B.;Yamamoto, Hisashi
我们发现乙醛的三(三甲基硅基)硅基(TTMSS)硅烯醇醚可以高选择性地进行醛交叉Aldol反应，并且极低的催化剂负载量(HNTf2的0.05mol%)允许一锅连续反应，随后可以添加酸性或碱性亲核试剂。各种酮衍生的硅烯醇醚、格氏试剂和双烯成功地在一步内产生了相对复杂的分子结构。这是第一种情况，在一个锅中，可以容忍高酸性条件和非常碱性的条件，以获得具有高非对映选择性和良好产率的产品。
We have shown that the tris(trimethylsilyl)silyl (TTMSS) silyl enol ether of acetaldehyde undergoes aldehyde cross-aldol reactions with high selectivity and the extremely low catalyst loading (0.05 mol % of HNTf2) allows for one-pot sequential reactions where acidic or basic nucleophiles can be subsequently added. Various ketone-derived silyl enol ethers, Grignard reagents, and dienes succeeded, generating relatively complex molecular architectures in a single step. This represents the first case where, in a single pot, highly acidic conditions followed by very basic conditions were tolerated to give products with high diastereoselectivities and good yields.