SELECTIVE CLEAVAGE OF ALLYL ETHERS UNDER MILD CONDITIONS BY TRANSITION-METAL REAGENTS
SELECTIVE CLEAVAGE OF ALLYL ETHERS UNDER MILD CONDITIONS BY TRANSITION-METAL REAGENTS
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DOI：
10.1021/jo00958a032
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发表时间：
1973-01-01
影响因子：
3.6
通讯作者：
SUGGS, JW
中科院分区：
文献类型：
--
作者：
COREY, EJ;SUGGS, JW
(1)对于涉及金属离子敏感保护基的早期应用，参见E，J. Corey和RL Dawson，J. Amer. Chem. Soc.，84，4899（1902）。条件烯醇醚2的水解在pH 2下迅速发生以形成游离醇3。对于甲醇、1-癸醇和胆固醇的烯丙基醚，证明了该方法的通用性，所有这些都可以容易地以> 90%的产率转化为相应的醇3。发现苄基醚在裂解烯丙基醚的条件下是稳定的。三三苯基膦氯化铑作为催化剂比RhCl 3，3活性高得多，而RhCl 3，3又比PdCl 2，RuCl 3或IrCl 3活性高。在这项工作之前，烯丙基醚的裂解已经通过使用强酸的常规方法，通过在乙酸-二氧六环中用Se 〇 2氧化，4或通过用强碱处理以产生烯醇醚，然后酸水解或氧化来实现。2· 5
(1) For an earlier application involving a metal-ion sensitive protecting group, see E, J. Corey and RL Dawson, J. Amer. Chem. Soc., 84, 4899 (1902). conditions. 2 Hydrolysis of the enol ethers 2 occurs rapidly at pH 2 to form the free alcohols 3. The generality of the process was demonstrated for the allyl ethers of methanol, 1-decanol, and cholesterol, all of which could be converted readily to the corresponding alcohols 3 in> 90% yield. Benzyl ethers were found to be stable under the conditions which cleave allyl ethers. Tristriphenylphosphine rhodium chloride was considerably more active as a catalyst than RhCl3, 3 which in turn was more active than PdCl2, RuC13, or IrCl3. Prior to this work the cleavage of allyl ethers has been effected by the conventional methodusing strong acids, by oxidation with Se02 in acetic acid-dioxane, 4 or by treatment with strong base to generate an enol ether followed by acid hydrolysis or oxidation. 2· 5