We are applying the developed [2+2+2] cyclotrimerization reactions to the rapid construction of libraries of biological pathway modifiers and small molecule fluorophores with new biological properties. In addition, we are demonstrating the applicability of the developed methods in the assembly of several structures found in nature. For example, we have been working on the synthesis of the natural products cryptoacetalide, citrinadine B, tylophorine, cannabinol, illudinine, and others.