Buchwald–Hartwig cross-coupling of amides (transamidation) by selective N–C(O) cleavage mediated by air- and moisture-stable [Pd(NHC)(allyl)Cl] precatalysts: catalyst evaluation and mechanism,Catalysis Science & Technology

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Buchwald–Hartwig cross-coupling of amides (transamidation) by selective N–C(O) cleavage mediated by air- and moisture-stable [Pd(NHC)(allyl)Cl] precatalysts: catalyst evaluation and mechanism
Catalysis Science & Technology ( IF 4.4 ) Pub Date : 2019/12/23 , DOI: 10.1039/c9cy02080b
Guangchen Li _{1,

2,

3,

4} , Tongliang Zhou _{1,

2,

3,

4} , Albert Poater _{5,

6,

7,

8} , Luigi Cavallo _{9,

10,

11,

12} , Steven P. Nolan _{1,

13,

14,

15} , Michal Szostak _{1,

2,

3,

4}

Affiliation

The Pd–NHC-catalyzed acyl-type Buchwald–Hartwig cross-coupling of amides by N–C(O) cleavage (transamidation) provides a valuable alternative to the classical methods for amide synthesis. Herein, we report a combined experimental and computational study of the Buchwald–Hartwig cross-coupling of amides using well-defined, air- and moisture-stable [Pd(NHC)(allyl)Cl] precatalysts. Most crucially, we present a comprehensive evaluation of a series of distinct Pd(II)–NHC precatalysts featuring different NHC scaffolds and throw-away ligands for the synthesis of functionalized amides that are not compatible with stoichiometric transition-metal-free transamidation methods. Furthermore, we present evaluation of the catalytic cycle by DFT methods for a series of different Pd(II)–NHC precatalysts. The viability of accessing NHC-supported acyl-palladium(II) amido complexes will have implications for the design and development of cross-coupling methods involving stable amide electrophiles.

中文翻译：

空气和水分稳定的[Pd（NHC）（烯丙基）Cl]预催化剂介导的选择性N–C（O）裂解引起的Buchwald–Hartwig酰胺交叉偶联（酰胺基转移反应）：催化剂评估和机理

通过N-C（O）裂解（酰胺基转移），Pd-NHC催化的酰胺基酰基型布赫瓦尔德-哈特维格交叉偶联为经典的酰胺合成方法提供了有价值的替代方法。本文中，我们报告了使用定义明确的，对空气和水分稳定的[Pd（NHC）（烯丙基）Cl]预催化剂进行的Buchwald-Hartwig酰胺交叉偶联的实验和计算研究。最关键的是，我们对一系列不同的Pd（II）-NHC预催化剂进行了全面评估，这些催化剂具有不同的NHC支架和可抛弃的配体，用于合成与化学计量无过渡金属的酰胺化方法不兼容的官能化酰胺。此外，我们目前通过DFT方法对一系列不同的Pd（II）的催化循环进行评估）– NHC预催化剂。获得NHC支持的酰基-钯（II）酰胺基配合物的可行性将对涉及稳定酰胺亲电试剂的交叉偶联方法的设计和开发产生影响。

更新日期：2020-02-13

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