Universität zu Köln

Stadler, Michael (2009). Heck reactions of Crotonaldehyde and Organocatalytic, asymmetric Mannich reactions of N-Boc and related imines. PhD thesis, Universität zu Köln.

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Abstract

This thesis is divided into two major parts. The first part deals with the development of conditions for a Heck reaction to introduce aryl and vinyl substituents to the beta-position of crotonaldehyde and related alpha,beta-unsaturated aldehydes. The reaction provides very fast (<1 h) access to the desired beta,beta-disubstituted, alpha,beta-unsaturated aldehydes in typically good to very high yields. The methodology is furthermore employed in shortening the formerly lengthy synthesis of enantiopure Florhydral. The second and larger part concerns the development of the chemistry of N-Boc, N-Cbz, N Fmoc, and N-Bz-imines in proline-catalyzed Mannich reactions of unmodified aldehydes and ketones. The reactions are usually good to high in yield and with high to excellent levels of enantioselectivity. It also describes the first use of acetaldehyde as donor in an organocatalyzed reaction, leading to defined single-addition products of extremely high enantiopurity. Finally, the newly developed methodology was employed to synthesize the side chain of paclitaxel (taxol), and the semisynthesis thereof is presented.

Item Type:	Thesis (PhD thesis)
Creators:	Creators Email ORCID ORCID Put Code Stadler, Michael mik.stadler@gmail.com UNSPECIFIED UNSPECIFIED
URN:	urn:nbn:de:hbz:38-27886
Date:	2009
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Ehemalige Fakultäten, Institute, Seminare > Faculty of Mathematics and Natural Sciences > no entry
Subjects:	Chemistry and allied sciences
Date of oral exam:	28 June 2009
Referee:	Name Academic Title List, Benjamin Prof. Dr.
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/2788