Catalytic diastereoselective petasis reactions.
Catalytic diastereoselective petasis reactions.
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DOI：
10.1002/anie.201103271
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发表时间：
2011-08-22
期刊：
影响因子：
--
通讯作者：
Schaus SE
中科院分区：
文献类型：
--
作者：
Muncipinto G;Moquist PN;Schreiber SL;Schaus SE
Petasis硼酸Mannich反应是硼酸、胺和醛的多组分反应，其产生高度官能化的α-氨基酸和β-氨基醇。[1]当使用对映体纯的α-羟基醛衍生物作为反应中的羰基组分时，对映体纯的β-氨基醇仅以反非对映体选择性生成。[2]该基序已被证明可用于合成立体定向的生物活性分子，包括唾液酸，[3]亚氨基环醇，[4]和吡咯里西啶生物碱。[5]使其有价值的非对映选择性硼酸曼尼希反应的特征，即其可预测的反非对映选择性意义，也是其限制，因为在这些条件下不能获得顺式β-氨基醇[Eq. 1]。[6]先前通过Petasis反应获得顺式β-氨基醇的尝试是不成功的，并且强调了克服反应的固有选择性的困难。[7]本文首次报道了手性联苯酚催化的非对映选择性Petasis反应，合成了纯的反式和顺式β-氨基醇。
The Petasis boronic acid Mannich reaction is a versatile multicomponent reaction of boronic acids, amines and aldehydes that generates highly functionalized α-amino acids and β-amino alcohols.[1] When enantiopure α-hydroxy aldehyde derivatives are used as the carbonyl component in the reaction, enantiopure β-amino alcohols are produced with exclusively anti diastereoselectivity.[2] This motif has proven useful in the synthesis of stereodefined, biologically active molecules including sialic acids,[3] iminocyclitols,[4] and pyrrolizidine alkaloids.[5] The characteristic of the diastereoselective boronic acid Mannich reaction that makes it valuable, namely its predictable sense of anti diastereoselectivity, is also its limitation as syn β-amino alcohols are unattainable under these conditions [Eq. 1].[6] Previous attempts to obtain syn β-amino alcohols via the Petasis reaction have been unsuccessful and underscore the difficulty in overriding the intrinsic selectivity of the reaction.[7] Herein, we report the first diastereoselective Petasis reaction catalyzed by chiral biphenols that enables the synthesis of anti and syn β-amino alcohols in pure form.