An iron variant of the Noyori hydrogenation catalyst for the asymmetric transfer hydrogenation of ketones.,Dalton Transactions

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An iron variant of the Noyori hydrogenation catalyst for the asymmetric transfer hydrogenation of ketones.
Dalton Transactions ( IF 3.5 ) Pub Date : 2020-05-14 , DOI: 10.1039/d0dt01204a
Shangfei Huo ₁ , Qingwei Wang , Weiwei Zuo

Affiliation

We report the design of a new iron catalyst for the asymmetric transfer hydrogenation of ketones. This type of iron catalyst combines the structural characteristics of the Noyori hydrogenation catalyst (an axially chiral 2,2′-bis(phosphino)-1,1′-binaphthyl fragment and the metal–ligand bifunctional motif) and an ene(amido) group that can activate the iron center. After activation by 8 equivalents of potassium tert-butoxide, (S_A,R_P,SS)-7a and (S_A,R_P,SS)-7b are active but nonenantioselective catalysts for the transfer hydrogenation of acetophenone and α,β-unsaturated aldehydes at room temperature in isopropanol. A maximum turnover number of 14480 was observed for (S_A,R_P,SS)-7a in the reduction of acetophenone. The right combination of the stereochemistry of the axially chiral 2,2′-bis(phosphino)-1,1′-binaphthyl group and the carbon-centered chiral amine-imine moiety in (S_A,R_P,RR)-7b′ afforded an enantioselective catalyst for the preparation of chiral alcohols with moderate to good yields and a broad functional group tolerance.

中文翻译：

Noyori加氢催化剂的铁变体，用于酮的不对称转移加氢。

我们报告了一种用于酮的不对称转移氢化的新型铁催化剂的设计。这类铁催化剂结合了Noyori氢化催化剂的结构特征（轴向手性2,2'-双（膦基）-1,1'-联萘片段和金属-配体双功能基序）和烯键（酰胺基）可以激活熨斗中心。在被8当量的叔丁醇钾激活后，（S _A，R _P，SS）-7a和（S _A，R _P，SS）-7b是在室温下在异丙醇中苯乙酮和α，β-不饱和醛转移氢化的活性但非对映选择性催化剂。（S _A，R _P，SS）-7a的苯乙酮还原反应最大翻转数为14480 。（S _A，R _P，RR）-7b'中的轴向手性2,2'-双（膦基）-1,1'-联萘基与碳中心手性胺-亚胺部分的立体化学的正确组合提供了用于制备手性醇的对映体选择性催化剂，具有中等至良好的收率和宽泛的官能团耐受性。

更新日期：2020-05-14

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