Universität zu Köln

Iniutina, Anna (2026). Catalytic Asymmetric Diels–Alder Reaction of β,β-Disubstituted Enals: Synthesis of (−)-(Z)-β-Santalol. PhD thesis, Universität zu Köln.

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Abstract

The Diels–Alder reaction remains a cornerstone of organic synthesis, enabling efficient construction of complex chiral frameworks. However, the enantioselective Diels–Alder reaction of β,β-disubstituted enals has long presented a formidable challenge due to the low dienophilicity and steric congestion of these substrates. In this work, we presenting the first general catalytic system for Diels–Alder reactions of this substrate class using strong imidodiphosphorimidate Brønsted acids. The optimized catalytic system displayed excellent robustness, reproducibility, and scalability, allowing for natural extension of this methodology to the concise total synthesis of (–)-(Z)-β-santalol, a key constituent of sandalwood oil. The synthetic route relies purely on bulk chemicals and delivers the target compound with excellent enantioselectivity in just five steps. Comprehensive mechanistic studies revealed the underlying principles responsible for the observed reactivity, and a complex cation exchange process between the imidodiphosphorimidates and molecular sieves.

Item Type:	Thesis (PhD thesis)
Creators:	Creators Email ORCID ORCID Put Code Iniutina, Anna ann.inyutina@gmail.com UNSPECIFIED UNSPECIFIED
URN:	urn:nbn:de:hbz:38-811867
Date:	2026
Language:	English
Faculty:	Faculty of Mathematics and Natural Sciences
Divisions:	Faculty of Mathematics and Natural Sciences > Department of Chemistry > Institute of Organic Chemistry
Subjects:	Chemistry and allied sciences
Uncontrolled Keywords:	Keywords Language asymmetric organocatalysis, imidodiphosphorimidates, Diels–Alder reaction, enals, β-santalol UNSPECIFIED
Date of oral exam:	27 January 2026
Referee:	Name Academic Title Benjamin, List Prof. Dr. Dumele, Oliver Prof. Dr.
Refereed:	Yes
URI:	http://kups.ub.uni-koeln.de/id/eprint/81186