Synthesis of Vallesamidine PresentedbyMitchellMaday

Background

• MonoterpeneindolealkaloidisolatedfromVallesiadichotoma

• Onlyracemicproductbeensynthesizedbefore

Goal

Forming the Nitro alkene

1,4 addi>on of Diethylmalonate

Lactamiza>on

Krapcho Decarboxyla>on

Allyla>on

Reduc>on of Nitro group

Cu and amino acid catalyzed coupling

Carbamate forma>on

2 Different Reduc>on pathways

Pathway A: create a thioamide

Thiolacam reduc>on

Aldehyde genera>on

Protec>ng the amine

Reduc>on pathway B

Protec>ng the Aldehyde

Amide reduc>on

Amine Protec>on

Aldehyde Deprotec>on

Internal decarboxyla>on

Amino acid catalyzed aldol

Mannich Cycliza>on

Ester reduc>on

Selec>ve Alcohol protec>on

Oxida>on to aldehyde

Alkene conversion and alcohol deprotec>on

Oxida>on to Aldehyde

Aldehyde to Alkene

Olefin Metathesis

Ester Reduc>on

Terminal alkene reduc>on

Conclusion

•  23stepsbutonly14chromatographicpurifica?ons

•  Firstreportedenan?opureVallesamidineproduct