I Ceric ammonium nitrate-mediated oxidative cleavages of hemiacetals II Synthesis of beta-proline derivatives through the tandem chain extension-imine capture reaction

<p>A novel ceric ammonium nitrate-mediated oxidative cleavage of hemiacetals generated through the use of the zinc carbenoid-mediated tandem chain extension-aldol reaction was developed. This chemistry has been applied towards the formation of a class of natural products, phaseolinic acids, in two steps from a commercially available beta-keto ester, methyl 4-methoxyacetoacetate.</p><p>The tandem chain extension-imine capture reaction has also been developed to provide access to beta-proline derivatives. Two activated imines were studied and provided access to different diastereomers, making the chemistry versatile. beta-Keto esters, beta-keto amides, and beta-keto imides were subjected to the tandem chain extension-imine capture reaction conditions and proved to be reasonably successful in most cases. beta-Keto esters were efficient in the synthesis of free --NH beta-proline derivatives in three steps and beta-keto imides were efficient in the synthesis of Boc-protected beta-proline derivatives in just two steps.</p><p>The zinc carbenoid-mediated chain extension imine capture reaction has developed into a flexible route in obtaining different diastereomers of protected and unprotected beta-proline derivatives in minimal steps from commercially available starting materials.</p>

Name thesis:degree_name

Doctor of Philosophy

Level thesis:degree_level

Dissertation

Year

2010

Author dc:creator

• Jacobine, Alexander M

Contributors dc:contributor

• Charles K Zercher

• Chemistry
• Organic

Repository record dc:identifier

https://scholars.unh.edu/dissertation/523

OAI identifier oai:identifier

oai:scholars.unh.edu:dissertation-1522