東華大學圖書館 |

語系: 繁體中文

說明(常見問題)

回圖書館首頁

手機版館藏查詢

登入

回首頁

切換: 標籤 | MARC模式 | ISBD

Palladium-Catalyzed Stereoselective ...

Ma, Qiao.

FindBook

Google Book

Amazon

博客來

Palladium-Catalyzed Stereoselective C-F Bond Activation of Gem-Difluoroalkenes and Copper-Mediated Trifluoromethylation of α-Diazo Compounds.

紀錄類型:	書目-電子資源 : Monograph/item
正題名/作者:	Palladium-Catalyzed Stereoselective C-F Bond Activation of Gem-Difluoroalkenes and Copper-Mediated Trifluoromethylation of α-Diazo Compounds./
作者:	Ma, Qiao.
出版者:	Ann Arbor : ProQuest Dissertations & Theses, : 2020,
面頁冊數:	371 p.
附註:	Source: Dissertations Abstracts International, Volume: 83-01, Section: B.
Contained By:	Dissertations Abstracts International83-01B.
標題:	Inorganic chemistry. -
電子資源:	https://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=28663005
ISBN:	9798505585177

Palladium-Catalyzed Stereoselective C-F Bond Activation of Gem-Difluoroalkenes and Copper-Mediated Trifluoromethylation of α-Diazo Compounds.
Ma, Qiao.

Palladium-Catalyzed Stereoselective C-F Bond Activation of Gem-Difluoroalkenes and Copper-Mediated Trifluoromethylation of α-Diazo Compounds. - Ann Arbor : ProQuest Dissertations & Theses, 2020 - 371 p.

Source: Dissertations Abstracts International, Volume: 83-01, Section: B.

Thesis (Ph.D.)--Hong Kong University of Science and Technology (Hong Kong), 2020.

Organofluorine compounds have gained increasing importance in medicine and material science. This is because the properties and reactivities of organic molecules can often be dramatically altered in the presence of fluorinated moieties. Therefore, there is a growing demand for the development of more efficient and selective methods to access fluorinated molecules. This thesis is divided into three parts detailing two palladium-catalyzed and one copper-mediated methods for the synthesis of novel fluorine-containing compounds. The first chapter describes a palladium-catalyzed Sonogashira process for the stereoselective synthesis of conjugated monofluoroenynes via the reaction of gemdifluoroalkenes with terminal alkynes. (Q. Ma, Y. Wang, G. C. Tsui, Angew. Chem. Int. Ed. 2020, 10.1002/anie.202002219.) This represents the first example of metalcatalyzed C-F bond alkynylation of gem-difluoroalkenes. In which, NaI as an additive plays a key role in the suppression of side reactions. Both NOE study and X-ray crystallography were used to confirm the E-configuration of the monofluoroenyne products. The successful preparation and crystallization of a key Pd complex provided direct evidence for the C-F bond insertion by Pd as a viable mechanistic pathway. The second chapter discusses a palladium-catalyzed stereoselective hydrodefluorination of gem-difluoroalkenes. (Q. Ma, C. Liu, G. C. Tsui, Org. Lett. 2020, 10.1021/acs.orglett.0c01813.) Hydrosilanes were used as the hydrogen source, with mild reaction conditions various monofluoroalkenes were obtained in good to high yields with excellent E-selectivity. The excellent level of stereocontrol presumably stems from an ester-directed C-F bond oxidative addition process. And a novel yield-enhancing effect of adding catalytic organic azide is also revealed. The formation of thermostable Si-F bond between Pd-F complex and hydrosilanes should be an important driving force to promote this reaction. The third chapter discloses a copper-mediated trifluoromethylation of α- diazoesters and α-diazoketones using fluoroform-derived CuCF3. (Q. Ma, G. C. Tsui, Org. Chem. Front. 2019, 6, 27−31.) Reaction conditions are mild and easy to handle, allowing the synthesis of a series of α-trifluoromethyl esters and ketones in one-step from α-diazo carbonyl compounds. The ultimate CF3 source is the inexpensive, nontoxic, industrial waste fluoroform. Synergistic effect of using 1,4-dioxane as cosolvent and pyridine as promoter is revealed.

ISBN: 9798505585177Subjects--Topical Terms:

3173556
Inorganic chemistry.
Subjects--Index Terms:

Organofluorine

Palladium-Catalyzed Stereoselective C-F Bond Activation of Gem-Difluoroalkenes and Copper-Mediated Trifluoromethylation of α-Diazo Compounds.
LDR:03617nmm a2200325 4500 001 2285102
005 20211124104352.5
008 220723s2020 ||||||||||||||||| ||eng d
020 $a 9798505585177
035 $a (MiAaPQ)AAI28663005
035 $a AAI28663005
040 $a MiAaPQ $c MiAaPQ
100 1 $a Ma, Qiao. $3 3564383
245 1 0 $a Palladium-Catalyzed Stereoselective C-F Bond Activation of Gem-Difluoroalkenes and Copper-Mediated Trifluoromethylation of α-Diazo Compounds.
260 1 $a Ann Arbor : $b ProQuest Dissertations & Theses, $c 2020
300 $a 371 p.
500 $a Source: Dissertations Abstracts International, Volume: 83-01, Section: B.
500 $a Advisor: Yeung, Ying Yeung;Sun, Jianwei.
502 $a Thesis (Ph.D.)--Hong Kong University of Science and Technology (Hong Kong), 2020.
520 $a Organofluorine compounds have gained increasing importance in medicine and material science. This is because the properties and reactivities of organic molecules can often be dramatically altered in the presence of fluorinated moieties. Therefore, there is a growing demand for the development of more efficient and selective methods to access fluorinated molecules. This thesis is divided into three parts detailing two palladium-catalyzed and one copper-mediated methods for the synthesis of novel fluorine-containing compounds. The first chapter describes a palladium-catalyzed Sonogashira process for the stereoselective synthesis of conjugated monofluoroenynes via the reaction of gemdifluoroalkenes with terminal alkynes. (Q. Ma, Y. Wang, G. C. Tsui, Angew. Chem. Int. Ed. 2020, 10.1002/anie.202002219.) This represents the first example of metalcatalyzed C-F bond alkynylation of gem-difluoroalkenes. In which, NaI as an additive plays a key role in the suppression of side reactions. Both NOE study and X-ray crystallography were used to confirm the E-configuration of the monofluoroenyne products. The successful preparation and crystallization of a key Pd complex provided direct evidence for the C-F bond insertion by Pd as a viable mechanistic pathway. The second chapter discusses a palladium-catalyzed stereoselective hydrodefluorination of gem-difluoroalkenes. (Q. Ma, C. Liu, G. C. Tsui, Org. Lett. 2020, 10.1021/acs.orglett.0c01813.) Hydrosilanes were used as the hydrogen source, with mild reaction conditions various monofluoroalkenes were obtained in good to high yields with excellent E-selectivity. The excellent level of stereocontrol presumably stems from an ester-directed C-F bond oxidative addition process. And a novel yield-enhancing effect of adding catalytic organic azide is also revealed. The formation of thermostable Si-F bond between Pd-F complex and hydrosilanes should be an important driving force to promote this reaction. The third chapter discloses a copper-mediated trifluoromethylation of α- diazoesters and α-diazoketones using fluoroform-derived CuCF3. (Q. Ma, G. C. Tsui, Org. Chem. Front. 2019, 6, 27−31.) Reaction conditions are mild and easy to handle, allowing the synthesis of a series of α-trifluoromethyl esters and ketones in one-step from α-diazo carbonyl compounds. The ultimate CF3 source is the inexpensive, nontoxic, industrial waste fluoroform. Synergistic effect of using 1,4-dioxane as cosolvent and pyridine as promoter is revealed.
590 $a School code: 1223.
650 4 $a Inorganic chemistry. $3 3173556
650 4 $a Mass spectrometry. $3 551172
650 4 $a Palladium. $3 644757
650 4 $a Protocol. $3 3564384
650 4 $a Fluorine. $3 1638042
650 4 $a Experiments. $3 525909
650 4 $a Carbon. $3 604057
650 4 $a Nuclear magnetic resonance--NMR. $3 3560258
650 4 $a Solvents. $3 620946
650 4 $a Optimization. $3 891104
650 4 $a Chemistry. $3 516420
650 4 $a Ligands. $3 686413
650 4 $a Scientific imaging. $3 3560377
650 4 $a Ratios. $3 3561161
650 4 $a Fluorides. $3 620981
650 4 $a Chromatography. $3 1073639
650 4 $a Peptides. $3 605772
650 4 $a Geometry. $3 517251
650 4 $a Crystallography. $3 518393
653 $a Organofluorine
653 $a Sonogashira
653 $a Difluoroalkenes
690 $a 0488
690 $a 0485
710 2 $a Hong Kong University of Science and Technology (Hong Kong). $3 1022235
773 0 $t Dissertations Abstracts International $g 83-01B.
790 $a 1223
791 $a Ph.D.
792 $a 2020
793 $a English
856 4 0 $u https://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=28663005