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Exploring C−H Functionalization Reac...

Omer, Humair Bin Md.

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Exploring C−H Functionalization Reactions with Theory and Experiment.

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Exploring C−H Functionalization Reactions with Theory and Experiment./
作者:	Omer, Humair Bin Md.
出版者:	Ann Arbor : ProQuest Dissertations & Theses, : 2020,
面頁冊數:	352 p.
附註:	Source: Dissertations Abstracts International, Volume: 82-06, Section: B.
Contained By:	Dissertations Abstracts International82-06B.
標題:	Chemistry. -
電子資源:	https://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=27736646
ISBN:	9798678117915

Exploring C−H Functionalization Reactions with Theory and Experiment.
Omer, Humair Bin Md.

Exploring C−H Functionalization Reactions with Theory and Experiment. - Ann Arbor : ProQuest Dissertations & Theses, 2020 - 352 p.

Source: Dissertations Abstracts International, Volume: 82-06, Section: B.

Thesis (Ph.D.)--University of Pittsburgh, 2020.

This item must not be sold to any third party vendors.

C−H bond functionalization reactions are powerful, efficient, and potentially step-economic strategy for the construction of carbon−carbon and carbon−heteroatom bonds in organic synthesis. In recent years, novel Ni-catalyzed C−H bond functionalization reactions using N,N bidentate directing groups have been developed to selectively activate inert C−H bonds. However, the reaction mechanisms and origins of reactivity and selectivity of many of these organic transformations remain unclear. A detailed understanding of the molecular processes involved is essential for understanding and developing more efficient and diverse C−H functionalization reactions. Density functional theory (DFT) has emerged as a powerful tool to elucidate reaction mechanisms and intricate details of the elementary steps involved, and divergent reaction pathways in transition metal-catalyzed reactions. In this dissertation, the mechanisms of Ni-catalyzed C-H oxidative annulation, arylation, alkylation, benzylation and sulfenylation with N,N-bidentate directing groups are investigated using DFT calculations. Ni-catalyzed C-H functionalization reactions can be broadly divided into two distinct mechanistic steps: (i) C-H metalation (ii) C-C or C-heteroatom bond formation steps. Specifically, the C-H metalation may occur via either the concerted metalation-deprotonation (CMD) or σ-complex-assisted metathesis (σ-CAM) mechanism. The subsequent C-C and C-heteroatom bond formation steps may occur via closed-shell Ni(II) or Ni(IV) intermediates. Alternatively, radical pathways involving Ni(III) complexes are also possible. Our studies indicated that the reaction mechanism of Ni-catalyzed C-H functionalization is substrate-dependent. The mechanistic insights gained from the computational studies were employed to investigate a number of experimental phenomena including substituent effects on reactivity, chemo- and regioselectivity, ligand and directing group effects, and the effects of oxidants. Furthermore, a novel C(sp3)−H functionalization methodology was developed to synthesize biologically relevant vinyl sulfone-containing compounds of pharmacologically prevalent picolyl amides with allenic sulfones. The reaction conditions are mild. The starting materials can be prepared from readily available sources. The reaction has a broad functional group tolerance. Mechanistic studies suggested that the reaction likely operates via a rare pyridine-initiated and p-toluenesulfinate anion-mediated activation analogous to phosphine-triggered reactions and Padwa's allenic sulfone chemistry.

ISBN: 9798678117915Subjects--Topical Terms:

516420
Chemistry.
Subjects--Index Terms:

C−H Functionalization

Exploring C−H Functionalization Reactions with Theory and Experiment.
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300 $a 352 p.
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500 $a Advisor: Liu, Peng;Brummond, Kay M.
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506 $a This item must not be sold to any third party vendors.
520 $a C−H bond functionalization reactions are powerful, efficient, and potentially step-economic strategy for the construction of carbon−carbon and carbon−heteroatom bonds in organic synthesis. In recent years, novel Ni-catalyzed C−H bond functionalization reactions using N,N bidentate directing groups have been developed to selectively activate inert C−H bonds. However, the reaction mechanisms and origins of reactivity and selectivity of many of these organic transformations remain unclear. A detailed understanding of the molecular processes involved is essential for understanding and developing more efficient and diverse C−H functionalization reactions. Density functional theory (DFT) has emerged as a powerful tool to elucidate reaction mechanisms and intricate details of the elementary steps involved, and divergent reaction pathways in transition metal-catalyzed reactions. In this dissertation, the mechanisms of Ni-catalyzed C-H oxidative annulation, arylation, alkylation, benzylation and sulfenylation with N,N-bidentate directing groups are investigated using DFT calculations. Ni-catalyzed C-H functionalization reactions can be broadly divided into two distinct mechanistic steps: (i) C-H metalation (ii) C-C or C-heteroatom bond formation steps. Specifically, the C-H metalation may occur via either the concerted metalation-deprotonation (CMD) or σ-complex-assisted metathesis (σ-CAM) mechanism. The subsequent C-C and C-heteroatom bond formation steps may occur via closed-shell Ni(II) or Ni(IV) intermediates. Alternatively, radical pathways involving Ni(III) complexes are also possible. Our studies indicated that the reaction mechanism of Ni-catalyzed C-H functionalization is substrate-dependent. The mechanistic insights gained from the computational studies were employed to investigate a number of experimental phenomena including substituent effects on reactivity, chemo- and regioselectivity, ligand and directing group effects, and the effects of oxidants. Furthermore, a novel C(sp3)−H functionalization methodology was developed to synthesize biologically relevant vinyl sulfone-containing compounds of pharmacologically prevalent picolyl amides with allenic sulfones. The reaction conditions are mild. The starting materials can be prepared from readily available sources. The reaction has a broad functional group tolerance. Mechanistic studies suggested that the reaction likely operates via a rare pyridine-initiated and p-toluenesulfinate anion-mediated activation analogous to phosphine-triggered reactions and Padwa's allenic sulfone chemistry.
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