Alternatives in the Design of Chemical Synthesis Combining

Alternatives in the Design of Chemical Synthesis • • • Combining process and medicinal chemistry Designing for all desired targets Avoiding unnecessary complication Home

Home Alternatives in the Design of Chemical Synthesis The Target Molecules Euthyroides episcopalis Cystodytes sp.

Home Alternatives in the Design of Chemical Synthesis Planning for Multiple Targets • Natural products are interconnected by virtue of their biosynthesis from ubiquitous starting materials

Home Alternatives in the Design of Chemical Synthesis Planning for Multiple Targets • In the case of new natural products the connectivity may be deduced based on our understanding of chemical reactivity

Alternatives in the Design of Chemical Synthesis Planning for Multiple Targets Home The Euthyroideones • Due to the unusual structural features of the euthyroideones they represent a trivial case of mapping

Alternatives in the Design of Chemical Synthesis Planning for Multiple Targets Home The Euthyroideones • Euthyroideones B and C appear to be oxidation products of euthyroideone A • However, since the overall structure shows a high • oxidation The hypothetical unsaturated euthyroideone state it may fully be assumed that B and C arise cannot beoxidation disregarded by further of A as a possible precursor

Alternatives in the Design of Chemical Synthesis Planning for Multiple Targets Deconstructing the Skeleton Home

Alternatives in the Design of Chemical Synthesis Planning for Multiple Targets Home Reaction Discovery Br 2 Conc. HCl It is important to remember that reagents may participate in multiple reaction types.

Alternatives in the Design of Chemical Synthesis Planning for Multiple Targets Reaction Discovery vs. This is particularly striking since it provides a means of differentiating the two reactive aromatic positions Home

Alternatives in the Design of Chemical Synthesis Planning for Multiple Targets Home Reaction Design ? ? ? Since the literature lacks a transformation capable of linking these two structures, we must move on to other approaches we must create one

Alternatives in the Design of Chemical Synthesis Planning for Multiple Targets Reaction Design The obstacle that presents itself in the elaboration of this structure is the reversibility of the Pictet-Spengler reaction Home

Alternatives in the Design of Chemical Synthesis Planning for Multiple Targets Home Reaction Design Replacing formaldehyde with glyoxilic acid provides a means of making the cyclization irreversible.

Alternatives in the Design of Chemical Synthesis Planning for Multiple Targets Home The Euthyroideones X The seemingly trivial methylation/oxidation necessary to complete this synthesis proved unworkable, and completion of the synthesis remains an elusive goal.

Alternatives in the Design of Chemical Synthesis Planning for Multiple Targets The Pyridoacridines Dopamine-derived pyridoacridine • Generalized pyridoacridine structure Home

Alternatives in the Design of Chemical Synthesis Mechanism for Synthesis The Pyridoacridine Family Home

Alternatives in the Design of Chemical Synthesis Planning for Multiple Targets The Pyridoacridines Dopamine-derived pyridoacridines Home

Alternatives in the Design of Chemical Synthesis Mechanism for Synthesis The Pyridoacridine Family Home

Alternatives in the Design of Chemical Synthesis Mechanism for Synthesis Styelsamine B Home

Alternatives in the Design of Chemical Synthesis The Big Picture • Take into account all desired target molecules as a guide to synthetic design • Be willing to explore new reaction chemistry • One unknown step may be preferable to several known steps Home

Alternatives in the Design of Chemical Synthesis Home Molecular Machines • It is possible to build molecular machinery off a surface using the caltrop previously synthesized in the Tour group 1 1. Jian, H. ; Tour, J. M. J. Org. Chem. 2003, 13, 5091 -5103.

Alternatives in the Design of Chemical Synthesis Molecular Machines • This tripod has previously been prepared by the chemistry described above Home

Alternatives in the Design of Chemical Synthesis Molecular Machines • The existing tripod synthesis is impractical and required improvement Home

Alternatives in the Design of Chemical Synthesis Molecular Machines • The previous tripod synthesis was completed by conversion of the protected alcohols to protected thiols for assembly on a gold surface Home

Home Alternatives in the Design of Chemical Synthesis Molecular Machines Nanocrane • From this base it is possible to construct a nanocrane for assembly on gold surfaces

Alternatives in the Design of Chemical Synthesis Nanocrane • The hinge portion of the nanocrane contains a photochemically active azobenzene Home

Alternatives in the Design of Chemical Synthesis Molecular Machines Nanocrane • By having a group which can be removed postassembly it may be possible to rapidly switch between different tips Home

Alternatives in the Design of Chemical Synthesis Molecular Machines Nanocrane • Coupling the Gen 2 crane tip to the caltrop base yields a soluble crane, albeit in low yield Home

Alternatives in the Design of Chemical Synthesis Molecular Machines Nanocrane • A SAM of cranes may ultimately prove the more practical application of these nanomachines Home

Alternatives in the Design of Chemical Synthesis Molecular Machines Nanocrane It may be possible to draw height features on the SAM using a narrow UV beam. Home