ChemInform Abstract: Pd‐Catalyzed Asymmetric Intramolecular Aryl C—O Bond Formation with SDP(O) Ligand: Enantioselective Synthesis of (2,3‐Dihydrobenzo[b][1,4]dioxin‐2‐yl)methanols.

Shi, Jialing; Wang, Ting; Huang, Yusha; Zhang, Xinhao; Wu, Yun‐Dong; Cai, Qian

doi:10.1002/chin.201528223

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“…The 1,1′-spirobiindane backbone (SDP(O)) ligand (49) coordinates to Pd to create an asymmetric chiral environment. 38 One of the hydroxyl groups binds with Pd to form a seven-membered ring (50). Twelve conformers of 50 were located.…”

Section: Reactionsmentioning

confidence: 99%

New Mechanistic Insights on the Selectivity of Transition-Metal-Catalyzed Organic Reactions: The Role of Computational Chemistry

2016

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With new advances in theoretical methods and increased computational power, applications of computational chemistry are becoming practical and routine in many fields of chemistry. In organic chemistry, computational chemistry plays an indispensable role in elucidating reaction mechanisms and the origins of various selectivities, such as chemo-, regio-, and stereoselectivities. Consequently, mechanistic understanding improves synthesis and assists in the rational design of new catalysts. In this Account, we present some of our recent works to illustrate how computational chemistry provides new mechanistic insights for improvement of the selectivities of several organic reactions. These examples include not only explanations for the existing experimental observations, but also predictions which were subsequently verified experimentally. This Account consists of three sections discuss three different kinds of selectivities. The first section discusses the regio- and stereoselectivities of hydrosilylations of alkynes, mainly catalyzed by [Cp*Ru(MeCN)3](+) or [CpRu(MeCN)3](+). Calculations suggest a new mechanism that involves a key ruthenacyclopropene intermediate. This mechanism not only explains the unusual Markovnikov regio-selectivity and anti-addition stereoselectivity observed by Trost and co-workers, but also motivated further experimental investigations. New intriguing experimental observations and further theoretical studies led to an extension of the reaction mechanism. The second section includes three cases of meta-selective C-H activation of aryl compounds. In the case of Cu-catalyzed selective meta-C-H activation of aniline, a new mechanism that involves a Cu(III)-Ar-mediated Heck-like transition state, in which the Ar group acts as an electrophile, was proposed. This mechanism predicted a higher reactivity for more electron-deficient Ar groups, which was supported by experiments. For two template-mediated, meta-selective C-H bond activations catalyzed by Pd(II), different mechanisms were derived for the two templates. One involves a dimeric Pd-Pd or Pd-Ag active catalyst, and the other involves a monomeric Pd catalyst, in which a monoprotected amino acid coordinates in a bidentate fashion and serves as an internal base for C-H activation. The third section discusses a desymmetry strategy in asymmetric synthesis. The construction of rigid skeletons is critical for these catalysts to distinguish two prochiral groups. Overall, fruitful collaborations between computational and experimental chemists have provided new and comprehensive mechanistic understanding and insights into these useful reactions.

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Section: Reactionsmentioning

confidence: 99%

New Mechanistic Insights on the Selectivity of Transition-Metal-Catalyzed Organic Reactions: The Role of Computational Chemistry

2016

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ChemInform Abstract: Pd‐Catalyzed Asymmetric Intramolecular Aryl C—O Bond Formation with SDP(O) Ligand: Enantioselective Synthesis of (2,3‐Dihydrobenzo[b][1,4]dioxin‐2‐yl)methanols.

Abstract: The method has been successfully applied in the syntheses of selective 5‐HT1A receptor agonist MKC‐242 (VIIIa) and selective α1D‐adrenoceptor inhibitor WB4101 (VIIIb).

Cited by 1 publication

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New Mechanistic Insights on the Selectivity of Transition-Metal-Catalyzed Organic Reactions: The Role of Computational Chemistry

New Mechanistic Insights on the Selectivity of Transition-Metal-Catalyzed Organic Reactions: The Role of Computational Chemistry

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