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首页> 外文期刊>Chemistry: A European journal >Highly efficient D _2 generation by dehydrogenation of formic acid in D _2O through H ~+/D ~+ exchange on an iridium catalyst: Application to the synthesis of deuterated compounds by transfer deuterogenation
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Highly efficient D _2 generation by dehydrogenation of formic acid in D _2O through H ~+/D ~+ exchange on an iridium catalyst: Application to the synthesis of deuterated compounds by transfer deuterogenation

机译：通过在铱催化剂上通过H〜+ / D〜+交换在D _2O中的甲酸脱氢来高效生成D _2：在转移氘代合成氘代化合物中的应用

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摘要

Deuterated compounds have received increasing attention in both academia and industrial fields. However, preparations of these compounds are limited for both economic and practical reasons. Herein, convenient generation of deuterium gas (D _2) and the preparation of deuterated compounds on a laboratory scale are demonstrated by using a half-sandwich iridium complex with 4,4'-dihydroxy-2,2'-bipyridine. The "umpolung" (i.e., reversal of polarity) of a hydrogen atom of water was achieved in consecutive reactions, that is, a cationic H ~+/D ~+ exchange reaction and anionic hydride or deuteride transfer, under mild conditions. Selective D _2 evolution (purity up to 89%) was achieved by using HCO _2H as an electron source and D _2O as a deuterium source; a rhodium analogue provided HD gas (98%) under similar conditions. Furthermore, pressurized D _2 (98%) without CO gas was generated by using DCO _2D in D _2O in a glass autoclave. Transfer deuterogenation of ketones gave α-deuterated alcohols with almost quantitative yields and high deuterium content by using HCO _2H in D _2O. Mechanistic studies show that the H ~+/D ~+ exchange reaction in the iridium hydride complex was much faster than β-elimination and hydride (deuteride) transfer. Cheap D _2 gas! Convenient generation of deuterium gas (D _2) and preparation of deuterated compounds on a laboratory scale are demonstrated using a half-sandwich iridium complex with 4,4'-dihydroxy-2,2'- bipyridine (see scheme). The "umpolung" of a hydrogen atom of water was achieved in consecutive reactions (cationic H ~+/D ~+ exchange reaction and anionic hydride (deuteride) transfer) under mild conditions.
机译：氘代化合物在学术界和工业领域都受到越来越多的关注。但是，由于经济和实际原因，这些化合物的制备受到限制。在此，通过使用具有4,4'-二羟基-2,2'-联吡啶的半夹心铱络合物，证明了方便的氘气（D _2）的产生和氘代化合物的实验室规模的制备。在温和的条件下，通过连续的反应，即阳离子H〜+ / D〜+交换反应和阴离子氢化物或氘代转移，实现了水的氢原子的“碰撞”（即极性反转）。通过使用HCO _2H作为电子源和D _2O作为氘源，实现了选择性的D _2析出（纯度高达89％）。铑类似物在类似条件下提供了高清气体（98％）。此外，通过在玻璃高压釜中在D _2O中使用DCO _2D产生了不带CO气体的加压D _2（98％）。通过在D _2O中使用HCO _2H，酮的转移氘代化制得的α-氘代醇几乎定量，且氘含量高。机理研究表明，氢化铱络合物中的H〜+ / D〜+交换反应比β-消除和氢化物（氘代）转移要快得多。便宜的D _2气！使用具有4,4'-二羟基-2,2'-联吡啶的半三明治铱络合物，证明了在实验室规模下方便地生成氘气（D _2）和制备氘代化合物的方法（请参见方案）。在温和的条件下，通过连续的反应（阳离子H〜+ / D〜+交换反应和阴离子氢化物（氘代）转移）实现了水氢原子的“化学计量”。

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