Palladium-Catalyzed C-H Bond Functionalization and Iron-Catalyzed Addition and Annulation Reactions

鈀金屬催化碳—氫鍵活化及鐵金屬催化加成及環化反應之研究

甘迪潘(GANDEEPAN)

指導教授 ： 鄭建鴻

國立清華大學/理學院/化學系/博士(2012年)

摘要

Transition metal-catalyzed direct transformations of inactivated CH bonds into various functional groups have emerged as a powerful method in organic synthesis. This methodology is fascinating for the chemical and pharmaceutical industries, because it can significantly simplify and shorten the synthetic route and also allow the utilization of less expensive, more readily available, and environmentally benign starting materials. Use of palladium complexes for CH bond functionalization to deduce new synthetic procedures which are more environmentally benign, atom efficient and economically viable than the existing methods was the motivation behind to the current works. With this regards, this thesis describes five new transformations (Chapter 1-5) for CC bond formation through CH bond activation using palladium catalyst.
Iron is 4th most abundant metal on earth and has been increasingly explored in modern catalysis to discover its unique and novel reactivity towards carbon–carbon and carbon–heteroatom bond formation. Owing to its inexpensive and environmentally friendly characteristics, considerable effort has been directed towards iron catalysis and as a result a series of novel iron-catalyzed organic transformations have been developed. Use of such low-cost and non-toxic iron complexes as catalysts in new CC and and Cheteroatom bond formation is highly desirable. With this concern, we also developed three new methods to synthesize -chlorovinyl ketones, ,-alkynyl ketones and 2,4-substituted Quinolines using iron-catalyzed reaction system (Chapter 6-7).

 Chapter 1 decribes the synthesis of phenanthrone derivatives from sec-alkyl aryl ketones with aryl iodides using palladium catalyst. The catalytic reaction appears to proceed via a dual CH activation and enolate cyclization.

 Chapter 2 depicts the synthesis of fluorenones by Pd-catalyzed oxidative cyclization of diaryl ketones. This methodology had advantages using readily available diaryl ketone starting materials to produce variety of fluorenones. This simple method offers an alternative and complimentary way to other fluorenone synthesis.

 Chapter 3 demonstrates an effective palladium-catalyzed carboncarbon double bond assisted selective ortho CH olefination of arenes at room temperature using dioxygen as the oxidant. The reaction appears to be the first example employing an allylic alkenyl double bond as a directing group for CH activation.

 Chapter 4 deals about the synthesis of substituted naphthalenes via palladium catalyzed CH activation and annulation of allyl arenes with alkynes. This reaction proceed through the -coordination of Pd(II) to the allylic carboncarbon double bond and ortho selective CH bond activation. The reaction adds an advantage to use environmentally friendly oxygen as a terminal oxidant.

 Chapter 5 showed an efficient and convenient method for the synthesis of symmetrically substituted 1,4-diaryl-1,3-butadienes by palladium-catalyzed oxidative dimerization of vinyl arenes. The reaction proceeds with broad substrate scope and excellent stereo selectivity.

 Chapter 6 elaborates the development of a very mild and convenient iron-catalyzed addition of acid chlorides to terminal alkynes to give the corresponding -chloroalkenyl ketones in very good yields with excellent regio- and stereoselectivity. The present iron-catalyzed addition reaction is successfully extended to alkynylsilanes to give alkynyl ketones.

 Chapter 7 reveals the synthesis of quinoline derivatives from iron catalyzed tandem reaction of aldimines with styrenes. This process can provide diverse range of quinoline derivatives in good to excellent yields from simple starting materials. The method has advantages of broad substrate scope, simple operation, mild reaction condition, and high effectiveness from non toxic and inexpensive iron catalyst. This reaction also extended to one-pot tandem three-component reaction of aldehydes, styrenes and amines to synthesis of quinoline derivatives.

關鍵字

鈀 ； 鐵 ； 碳—氫鍵活化 ； 加成反應 ； 環化反應

並列摘要

無資料

並列關鍵字

PALLADIUM ； IRON ； C-H ACTIVATION ； ADDITION REACTION ； ANNULATION REACTION

參考文獻

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