Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date:...
Transcript of Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date:...
![Page 1: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/1.jpg)
Synthesis of Vallesamidine PresentedbyMitchellMaday
![Page 2: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/2.jpg)
![Page 3: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/3.jpg)
Background
• MonoterpeneindolealkaloidisolatedfromVallesiadichotoma
• Onlyracemicproductbeensynthesizedbefore
![Page 4: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/4.jpg)
Goal
![Page 5: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/5.jpg)
Forming the Nitro alkene
![Page 6: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/6.jpg)
1,4 addi>on of Diethylmalonate
![Page 7: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/7.jpg)
Lactamiza>on
![Page 8: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/8.jpg)
Krapcho Decarboxyla>on
![Page 9: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/9.jpg)
Allyla>on
![Page 10: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/10.jpg)
Reduc>on of Nitro group
![Page 11: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/11.jpg)
Cu and amino acid catalyzed coupling
![Page 12: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/12.jpg)
Carbamate forma>on
![Page 13: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/13.jpg)
2 Different Reduc>on pathways
![Page 14: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/14.jpg)
Pathway A: create a thioamide
![Page 15: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/15.jpg)
Thiolacam reduc>on
![Page 16: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/16.jpg)
Aldehyde genera>on
![Page 17: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/17.jpg)
Protec>ng the amine
![Page 18: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/18.jpg)
Reduc>on pathway B
![Page 19: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/19.jpg)
Protec>ng the Aldehyde
![Page 20: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/20.jpg)
Amide reduc>on
![Page 21: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/21.jpg)
Amine Protec>on
![Page 22: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/22.jpg)
Aldehyde Deprotec>on
![Page 23: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/23.jpg)
Internal decarboxyla>on
![Page 24: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/24.jpg)
Amino acid catalyzed aldol
![Page 25: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/25.jpg)
Mannich Cycliza>on
![Page 26: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/26.jpg)
Ester reduc>on
![Page 27: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/27.jpg)
Selec>ve Alcohol protec>on
![Page 28: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/28.jpg)
Oxida>on to aldehyde
![Page 29: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/29.jpg)
Alkene conversion and alcohol deprotec>on
![Page 30: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/30.jpg)
Oxida>on to Aldehyde
![Page 31: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/31.jpg)
Aldehyde to Alkene
![Page 32: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/32.jpg)
Olefin Metathesis
![Page 33: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/33.jpg)
Ester Reduc>on
![Page 34: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/34.jpg)
Terminal alkene reduc>on
![Page 35: Maday - Chemistry · 2020. 1. 29. · Title: Maday.pptx Author: William Wulff Created Date: 20200129194439Z](https://reader036.fdocuments.net/reader036/viewer/2022071115/5ffb82fe73edb61d1567dd23/html5/thumbnails/35.jpg)
Conclusion
• 23stepsbutonly14chromatographicpurifica?ons
• Firstreportedenan?opureVallesamidineproduct