Highly Enantioselective Vinyl Additions of Vinylaluminum to Ketones Catalyzed by a Titanium(IV) Catalyst of (S)-BINOL
Highly Enantioselective Vinyl Additions of Vinylaluminum to Ketones Catalyzed by a Titanium(IV) Catalyst of (S)-BINOL
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DOI：
10.1021/ol801999u
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发表时间：
2009-02-05
期刊：
影响因子：
5.2
通讯作者：
Gau, Han-Mou
中科院分区：
文献类型：
--
作者：
Biradar, Deepak Baburao;Gau, Han-Mou
我们报道了一种新型的乙烯基不对称加成反应，使用乙烯基铝试剂，由原位制备的 (S)-BINOL 的 Ti(O'Pr)(4) 配合物催化，得到多样化的叔烯丙醇。对芳香环上带有给电子或吸电子取代基的各种芳香酮进行了研究，以提供具有高达 98% ee 的优异对映选择性和高收率的产品。 10 倍的放大反应以相似的产率和相当的对映选择性提供了产物。更重要的是，证明了添加包括官能化乙烯基在内的各种乙烯基试剂，可以提供具有高达 96% ee 的良好至优异对映选择性的叔烯丙醇。
We report a novel asymmetric addition of vinyl group to ketones using vinylaluminum reagents catalyzed by in situ prepared Ti(O'Pr)(4) complexes of (S)-BINOL to afford diversified tertiary allylic alochols. Varieties of aromatic ketones bearing either an electron-donating or an electron-withdrawing substituent on the aromatic ring were examined to afford products in excellent enantioselectivities of up to 98% ee with high yields. A 10-fold scale-up reaction afforded the product in a similar yield with a comparable enantioselectivity. More importantly, additions of a variety of vinyl reagents including functionalized vinyls were demonstrated, affording tertiary allylic alcohols with good to excellent enantioselectivities of up to 96% ee.