钯烯醇化物反转：Pd/SPRIX 催化剂促进的炔基环己二烯酮的环化二乙酰氧化。
Palladium enolate umpolung: cyclative diacetoxylation of alkynyl cyclohexadienones promoted by a Pd/SPRIX catalyst.
机构信息
The Institute of Scientific and Industrial Research (ISIR), Osaka University, Mihogaoka, Ibaraki-shi, Osaka 567-0047 (Japan).
出版信息
Angew Chem Int Ed Engl. 2014 Apr 25;53(18):4675-9. doi: 10.1002/anie.201311172. Epub 2014 Mar 26.
A novel palladium-catalyzed reaction involving an unusual nucleophilic attack on a palladium enolate was developed using a spiro-bis(isoxazoline) (SPRIX) ligand. Treatment of alkynyl cyclohexadienone substrates with a Pd/SPRIX catalyst in acetic acid under an oxygen atmosphere furnished diacetoxylated benzofuranone derivatives in good yields. This cyclative diacetoxylation proceeded enantioselectively in the presence of an optically pure SPRIX ligand.
一种新型钯催化反应，涉及到钯烯醇化物上的一种不寻常的亲核进攻，使用了螺双（异恶唑啉）（SPRIX）配体。在氧气气氛下，用 Pd/SPRIX 催化剂在乙酸中处理炔基环己二烯酮底物，以良好的收率得到二乙酰氧基苯并呋喃酮衍生物。在光学纯 SPRIX 配体的存在下，这种环化二乙酰氧基化反应具有对映选择性。
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