School of Science Department of Chemistry 5 Medicinal Chemistry on Novel Type I1/2 ALK Inhibitors for Combating Drug-Resistant Mutants Supervisor: HUANG Yong / CHEM Student: LU Yuheng / CHEM Course: UROP 1100, Spring UROP 2100, Summer Diazo compounds, pioneered by Peter Griess in 1858 through diazonium intermediate synthesis, serve as fundamental carbene precursors in organic synthesis. Upon thermolysis, photolysis, or transition-metal catalysis, these compounds release nitrogen gas to generate reactive carbenes (R₁R₂C:) or metallcarbene (R₁R₂C=M), enabling diverse bond-forming transformations. Various applications including cyclopropanation, olefination, rearrangement were the main focus of study since last century, while C-H or X-H insertion was brought onto stage during the past decade. However, the synthetic difficulty of diazo compounds hindered the expansion of building block library. A general method for synthesis of various types of diazo compounds was introduced, which could overcome the lack of compatibility of existing methods UROP1100_Medicinal Chemistry on Novel Type I1/2 ALK Inhibitors for Combating Drug-resistant Mutants towards diazo compounds with various electronic properties. In the last, synthesis of N-tosylhydrazones was also achieved, providing an alternating approach. Synthesis, Reactivity and Catalytic Properties of Transition Metal Carbyne Complexes Supervisor: JIA Guocheng / CHEM Student: TSUI Chun Pan / CHEM Course: UROP 1100, Spring Rhenium(V) alkylidyne complex Re(≡CCH2Ph)(PO)2(H2O), featuring phosphino-phenolate ligands, effectively catalyzes ring-closing alkyne metathesis (RCAM) of terminal-internal alkynes, forming macrocycles consisting of 12 to 25 member rings (C12-C25) under optimized conditions. High yields (98%) of a C25 macrocycle were achieved, while a C15 macrocycle faced competitive dimerization, indicating size-dependent kinetic challenges. Conjugated aromatic substrates were unreactive, suggesting steric or electronic limitations. Terminal-terminal alkynes showed significantly lower reactivity despite harsher conditions. This study elucidates the scope and limitations of Re(V)-catalyzed RCAM, providing insights for future catalyst design aimed at overcoming steric and electronic barriers in macrocycle synthesis. Synthesis, Reactivity and Catalytic Properties of Transition Metal Carbyne Complexes Supervisor: JIA Guocheng / CHEM Student: TUNG Kwun Fung / CHEM Course: UROP 1100, Spring Osmium can form alkylidyne complexes with a non-d0 metal center (low-valent). One of the most interesting properties of alkylidyne complexes is that they can undergo or mediate metathesis reactions. The metathesis activity of the dichloro carbyne complexes OsCl2(≡CR)(H)(PPh3)2 (R=p-tolyl) were studied. Treatment of OsCl2(≡CR)(H)(PPh3)2 (R=p-tolyl) with PCy3 produced OsCl2(≡CR)(H)(PPh3)2 (R=p-tolyl). While both OsCl2(≡CR)(H)(PPh3)2 (R=p-tolyl) and OsCl2(≡CR)(H)(PPh3)2 (R=p-tolyl) react with PhICl2 to produce OsCl3(≡CR)(PCy3)2 (R=p-tolyl) and OsCl3(≡CR)(PPh3)2 (R=p-tolyl) respectively. Reactions of OsCl3(≡CR)(PPh3)2 (R=p-tolyl) with PO and PS gave OsCl2(≡CR)(PO)(PPh3) (R=p-tolyl) and OsCl(≡CR)(PS)2 (R=p-tolyl) respectively, but do not reacted with PN ligand. Stoichiometric reaction of OsCl2(≡CR)(PO)(PPh3) (R=p-tolyl) with different alkyne (both internal and terminal alkynes) were carried out.
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