实用且广泛适用的烯丙基-B(pin)化合物对酮和α-酮酯的催化对映选择性加成。
Practical and Broadly Applicable Catalytic Enantioselective Additions of Allyl-B(pin) Compounds to Ketones and α-Ketoesters.
机构信息
Department of Chemistry, Merkert Chemistry Center, Boston College, Chestnut Hill, MA 02467 (USA).
出版信息
Angew Chem Int Ed Engl. 2016 Aug 8;55(33):9610-9614. doi: 10.1002/anie.201603894. Epub 2016 Jun 7.
Abstract
A set of broadly applicable methods for efficient catalytic additions of easy-to-handle allyl-B(pin) (pin=pinacolato) compounds to ketones and acyclic α-ketoesters was developed. Accordingly, a large array of tertiary alcohols can be obtained in 60 to >98 % yield and up to 99:1 enantiomeric ratio. At the heart of this development is rational alteration of the structures of the small-molecule aminophenol-based catalysts. Notably, with ketones, increasing the size of a catalyst moiety (tBu to SiPh3 ) results in much higher enantioselectivity. With α-ketoesters, on the other hand, not only does the opposite hold true, since Me substitution leads to substantially higher enantioselectivity, but the sense of the selectivity is reversed as well.
摘要
开发了一套广泛适用于将易于处理的烯丙基-B(pin)（pin=频哪醇酯）化合物高效催化加成到酮和非环α-酮酯的方法。因此，可以以 60 至 >98%的产率和高达 99:1 的对映体比率获得大量的叔醇。这一发展的核心是合理改变基于小分子氨基酚的催化剂的结构。值得注意的是，对于酮，增大催化剂部分（tBu 到 SiPh3）的尺寸会导致更高的对映选择性。另一方面，对于α-酮酯，情况并非如此，因为 Me 取代会导致对映选择性大大提高，而且选择性的方向也会反转。
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