Nature Catalysis ( IF 42.8 ) Pub Date : 2024-07-26 , DOI: 10.1038/s41929-024-01203-7 Francesco Zamberlan
They first established that, in dimethyl sulfoxide (DMSO), the alkyl bromide can act as a catalyst in the transfer of a chlorine atom from an alkyl chloride to the α-carbon of a carbonyl compound. This was further confirmed by mechanistic investigations, which enabled the team to propose a sequence of events where the halogenated compound reacts with DMSO at high temperature to yield an alkoxysulfonium salt that hydrolyses to the corresponding alcohol and hydrogen halide. Then, acidic conditions and DMSO oxidize the bromide ion to Br+, which is attacked by the enol to yield the brominated ketone; this eventually reacts with the free chlorine in a halogen-exchange reaction, regenerating the bromide ion and producing the α-chlorinated ketone.
In fact, several alkyl bromides can act as catalyst, particularly primary or secondary alkyl such as iso-propyl bromide, while benzyl chloride was a good chlorine-transfer reagent. The team also showed that ketones presenting low steric hindrance easily reacted under these conditions to yield α-chloroketones. As the ketone isomerizes to enol before chlorination, the researchers exploited this to chlorohydroxylate aryl-conjugated olefins using benzyl chloride in the presence of catalytic amounts of hydrobromic acid and radical polymerization inhibitors.
中文翻译:
有机污染物的再利用
他们首先确定,在二甲基亚砜 (DMSO) 中,烷基溴可以充当催化剂,将氯原子从烷基氯转移到羰基化合物的 α-碳上。机理研究进一步证实了这一点,使该团队能够提出一系列事件,其中卤代化合物与 DMSO 在高温下反应生成烷氧基锍盐,该盐水解成相应的醇和卤化氢。然后,酸性条件和DMSO将溴离子氧化为Br + ,Br + 被烯醇攻击生成溴化酮;最终在卤素交换反应中与游离氯发生反应,重新生成溴离子并产生 α-氯化酮。
事实上,几种烷基溴可以充当催化剂,特别是伯烷基或仲烷基,例如异丙基溴,而苄基氯是良好的氯转移试剂。研究小组还表明,具有低空间位阻的酮在这些条件下很容易发生反应,生成 α-氯酮。由于酮在氯化前异构化为烯醇,研究人员利用这一点,在催化量的氢溴酸和自由基聚合抑制剂存在下,使用苄基氯对芳基共轭烯烃进行氯羟基化。