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You searched for subject:(benzylpalladium). Showing records 1 – 2 of 2 total matches.

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University of California – Irvine

1. Gutman, Eugene. Development of C-C and C-N Bond Forming Reactions Utilizing Palladium Carbene Intermediates and Reaction Predictor: Using Machine Learning to Help Identify Unknown Side-Products in Organic Reactions.

Degree: Chemistry, 2017, University of California – Irvine

The research described herein consists of two disparate areas of study. The first and largest portion describes the development of novel palladium-catalyzed C-C and C-N bond forming reactions. The second portion describes the development of the Reaction Predictor system and its application towards identification of reaction products and pathways. Palladium-carbenes are important intermediates in many modern C-C and C-heteroatom bond forming reactions. Palladium-catalyzed carbenylative coupling reactions are analogous to carbonylative processes with carbon monoxide. Insertion of a cis X type ligand into the palladium-carbene can potentially generate a new stereogenic center, making these reactions worthy of study. Carbenylative insertions have been used to generate electrophilic η3- allylpalladium species which were trapped with nitrogen and carbon nucleophiles. This work describes the cyclization of η3-benzylpalladium species derived from palladium-catalyzed carbenylative insertion. This optimization and broad substrate scope of this reaction led to the synthesis of 1-arylindanes and 1-aryltetralins in high yields. Additionally, this reaction was used to prepare tetralone 2.30bl, a synthetic intermediate in the Curran synthesis of (±)-podophyllotoxin. The carbenylative cyclization also led us to pursue utilizing aliphatic N-tosylhydrazones as palladium-carbene precursors in other coupling reactions. It was realized that aliphatic N-tosylhydrazones with adjacent hydrogens can effectively participate in three-component palladium-catalyzed carbenylative cross-coupling reactions of vinyl iodides while avoiding β-hydride elimination. Development of a palladium-catalyzed enantioselective carbene insertion into the N-H bond of aromatic heterocycles to obtain α-(N-indolyl)-α-arylesters and α-(N-carbazolyl)-α-arylesters, using α-diazo-α-arylacetates as palladium carbene precursors is also described. Aliphatic amines were also competent coupling partners in the reaction, affording biologically active piperdine derivatives in moderate yields. The reaction was applied towards the synthesis of a bioactive carbazole derivative in a concise manner. In a separate project an inductive machine learning reaction prediction program called Reaction Predicator has been trained and applied towards identification of plausible reaction products in ESI spectra. The reaction predictor training set has been expanded by the addition of new reactions written in our lab. Over 800 transition metal based training reactions have been written. In addition, over 10,000 new complex training reactions have been written and added to the training set. The Reaction Predictor pathway search feature has been customized to match products to unknown m/z peaks in ESI spectra. Pathway search was applied towards unknown identification in palladium-catalyzed N-H insertion reactions.

Subjects/Keywords: Organic chemistry; benzylpalladium; carbene; Gutman; indane; palladium; tetralin

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6th Edition):

Gutman, E. (2017). Development of C-C and C-N Bond Forming Reactions Utilizing Palladium Carbene Intermediates and Reaction Predictor: Using Machine Learning to Help Identify Unknown Side-Products in Organic Reactions. (Thesis). University of California – Irvine. Retrieved from http://www.escholarship.org/uc/item/07p2s268

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Chicago Manual of Style (16th Edition):

Gutman, Eugene. “Development of C-C and C-N Bond Forming Reactions Utilizing Palladium Carbene Intermediates and Reaction Predictor: Using Machine Learning to Help Identify Unknown Side-Products in Organic Reactions.” 2017. Thesis, University of California – Irvine. Accessed August 06, 2020. http://www.escholarship.org/uc/item/07p2s268.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

MLA Handbook (7th Edition):

Gutman, Eugene. “Development of C-C and C-N Bond Forming Reactions Utilizing Palladium Carbene Intermediates and Reaction Predictor: Using Machine Learning to Help Identify Unknown Side-Products in Organic Reactions.” 2017. Web. 06 Aug 2020.

Vancouver:

Gutman E. Development of C-C and C-N Bond Forming Reactions Utilizing Palladium Carbene Intermediates and Reaction Predictor: Using Machine Learning to Help Identify Unknown Side-Products in Organic Reactions. [Internet] [Thesis]. University of California – Irvine; 2017. [cited 2020 Aug 06]. Available from: http://www.escholarship.org/uc/item/07p2s268.

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation

Council of Science Editors:

Gutman E. Development of C-C and C-N Bond Forming Reactions Utilizing Palladium Carbene Intermediates and Reaction Predictor: Using Machine Learning to Help Identify Unknown Side-Products in Organic Reactions. [Thesis]. University of California – Irvine; 2017. Available from: http://www.escholarship.org/uc/item/07p2s268

Note: this citation may be lacking information needed for this citation format:
Not specified: Masters Thesis or Doctoral Dissertation


University of Utah

2. Liao, Longyan. Development of palladium-catalyzed difunctionalization reactions of 1,3-dienes and alkenes.

Degree: PhD, Chemistry, 2012, University of Utah

Palladium (Pd)-catalyzed alkene difunctionalization reactions have been an active area of research in recent years. Expanding the diversity of alkene functionalization reactions to strategically impact the synthesis of small, complex molecules has been a long-standing area ofinterest for our group. In order to accomplish such transformations in palladium-catalyzed systems, the control of competing P-hydride elimination of Pd-alkyl intermediates must be achieved. One strategy employed to circumvent P-hydride elimination is substrate control via nallylpalladium or n-benzylpalladium intermediates, which may themselves be subsequently functionalized. Described below are several catalytic systems that we have developed based on this strategy to achieve the difunctionalization of 1,3-dienes and terminal alkenes.In the first chapter, an introduction to palladium-catalyzed alkene functionalization reactions utilizing substrate control via n-allylpalladium or n-benzylpalladium intermediates is presented. It is shown that these intermediates have been accessed in situ in a number of ways to facilitate non-Heck-type alkene functionalization reactions.In Chapter 2, our approach to the 1,2-hydroarylation of 1,3-dienes through the direct generation of n-allylpalladium intermediates via migratory insertion of 1,3-dienes into Pd-aryl species is described. Utilizing related strategies, the 1,2-vinylarylation (Chapter 3), and 1,2-diarylation (Chapter 4) of 1,3-dienes have been successfully developed. Additionally, by employing the generation of n-allylpalladium and n-benzylpalladium intermediates via hydride rearrangement, the 1,1-vinyarylation (Chapter 3) and 1,1-diarylation (Chapter 5) of simple alkenes have also been accomplished.

Subjects/Keywords: 1,3-dienes; Difunctionalization; Palladium-catalyzed; Allylpalladium; Benzylpalladium; Terminal alkenes

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APA · Chicago · MLA · Vancouver · CSE | Export to Zotero / EndNote / Reference Manager

APA (6th Edition):

Liao, L. (2012). Development of palladium-catalyzed difunctionalization reactions of 1,3-dienes and alkenes. (Doctoral Dissertation). University of Utah. Retrieved from http://content.lib.utah.edu/cdm/singleitem/collection/etd3/id/3453/rec/715

Chicago Manual of Style (16th Edition):

Liao, Longyan. “Development of palladium-catalyzed difunctionalization reactions of 1,3-dienes and alkenes.” 2012. Doctoral Dissertation, University of Utah. Accessed August 06, 2020. http://content.lib.utah.edu/cdm/singleitem/collection/etd3/id/3453/rec/715.

MLA Handbook (7th Edition):

Liao, Longyan. “Development of palladium-catalyzed difunctionalization reactions of 1,3-dienes and alkenes.” 2012. Web. 06 Aug 2020.

Vancouver:

Liao L. Development of palladium-catalyzed difunctionalization reactions of 1,3-dienes and alkenes. [Internet] [Doctoral dissertation]. University of Utah; 2012. [cited 2020 Aug 06]. Available from: http://content.lib.utah.edu/cdm/singleitem/collection/etd3/id/3453/rec/715.

Council of Science Editors:

Liao L. Development of palladium-catalyzed difunctionalization reactions of 1,3-dienes and alkenes. [Doctoral Dissertation]. University of Utah; 2012. Available from: http://content.lib.utah.edu/cdm/singleitem/collection/etd3/id/3453/rec/715

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