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The Washington Research Foundation Fellowship

Jeremy Housekeeper, Chemistry

Jeremy Housekeeper Jeremy Housekeeper is a senior studying Chemistry and Biochemistry.

Jeremy Housekeeper began his research career during the summer following freshman year in the lab of Professor Christine K. Luscombe. As part of Professor Luscombe's lab in Materials Science and Engineering, he is working on the development of next-generation materials and synthetic techniques for organic electronics applications.

His current project focuses on the synthesis of dithienothiophene (DTT) and other molecules through C-H activation. C-H activation is an emerging catalytic methodology that eschews the use of traditional organometallic-functionalized precursors. Through C-H activation, compounds can be synthesized in fewer steps and with significantly reduced environmental impact.

With support from the WRF Fellowship, Jeremy is looking to further develop C-H activation methodologies so that DTT and similarly complex compounds can be made both cheaply and easily.

Mentor: Christine Luscombe, Materials Science & Engineering

Project Title: Heterocycle Synthesis through a C-H Activation Cascade Reaction

Abstract: Until recently, little research has been done on C-S bond formation in transition-metal catalyzed transformations compared to other carbon-heteroatom bonds such as C-N, C-O, and C-P. As sulfur-based coupling partners (thiol and disulfide for example) tend to poison transition-metal catalysts, development of C-S bond formation has been slow. However, a recent nickel-catalyzed system shed new light on this difficult transformation. In this context, C-H functionalization is a sustainable and straightforward approach to sulfur-containing heteroaromatic production. C-H activation is a process whereby a carbon-hydrogen bond is cleaved, thereby allowing the exposed carbon atom to form new bonds. Thus, in order to expand the above research of C-S bond formation toward development of short synthesis for fused thiophene systems, focus was placed on a palladium catalyzed cascade-type reaction system. C-H activation reactions can and have been manipulated to work in a cascade-type fashion. By combining cascade-type methodology with the reduced environmental impact of C-H activation, these fused thiophenes can be synthesized cleanly and efficiently. The test substrates in this work are O,O-diethyl S-phenyl phosphorothioate and 4,4,5,5-tetramethyl-2-(thiophen-2-yl)-1,3,2-dioxaborolane. Both substrates were chosen because they contain sulfur, thereby aiding the C-H activation process. By effecting a C-H activation with a palladium catalyst at one of the ortho carbons of the phenyl ring with the boronic ester of the thiophene, the first C-C bond will be formed. In the time immediately after this first transformation, the now-changed palladium complex is able to insert into the S-P bond of the phenyl-based compound. This step sets up the second reaction, whereby the phosphorothioate directing group is cleaved along the S-P bond and the resulting thiol is coupled to a carbon atom to close the ring. This molecule is known as benzo[b]thieno[2,3-d]thiophene.