Universität zu Köln

Berkessel, Albrecht, Vormittag, Sonja S., Schloerer, Nils E. and Neudoerfl, Joerg-M (2012). TEFDDOLs (alpha,alpha,alpha ',alpha '-Tetrakis(perfluoroaryl/alkyl)-2,2 '-dimethyl-1,3-dioxolane-4,5-dimethanols): Highly Fluorinated Chiral H-Bond Donors and Bronsted Acids with Distinct H-Bonding Patterns and Supramolecular Architectures. J. Org. Chem., 77 (22). S. 10145 - 10158. WASHINGTON: AMER CHEMICAL SOC. ISSN 1520-6904

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Abstract

The synthesis of six enantiopure alpha,alpha,alpha',alpha'-tetrakis(perfluoroalkyl/aryl)-2,2' -dimethyl-1,3-dioxolane-4,5-dimethanols (TEFDDOLs), by addition of perfluorinated organolithium reagents or Ruppert's reagent (TMS-CF3) to isopropylidene tartaric dichloride, is reported. X-ray crystal structures of the TEFDDOLs alone or in complexes with H-bond acceptors such as water and DABCO revealed that this new class of highly fluorinated chiral 1,4-diols forms distinct intra- and intermolecular H-bond patterns. Intramolecular OH-OH bonding accounts for the relatively high acidity of the perfluoroalkyl TEFDDOLs (pK(a) in DMSO: tetrakis-CF3, 5.7; tetrakis-C2F5, 2.4). For the tetrakis(perfluorophenyl) TEFDDOL, a quite unusual pseudo-anti conformation of the diol, with no intramolecular (and no intermolecular) OH-OH bonds, was found both in the crystal and in solution (DOSY and NOESY NMR). The latter conformation results from a total of four intramolecular OH-F-aryl, hydrogen bonds overriding OH-OH bonding. Due to their H-bonding properties, the TEFDDOLs are promising new building blocks for supramolecular and potentially catalytic applications.

Item Type:	Journal Article
Creators:	Creators Email ORCID ORCID Put Code Berkessel, Albrecht UNSPECIFIED UNSPECIFIED UNSPECIFIED Vormittag, Sonja S. UNSPECIFIED UNSPECIFIED UNSPECIFIED Schloerer, Nils E. UNSPECIFIED UNSPECIFIED UNSPECIFIED Neudoerfl, Joerg-M UNSPECIFIED UNSPECIFIED UNSPECIFIED
URN:	urn:nbn:de:hbz:38-478865
DOI:	10.1021/jo301609g
Journal or Publication Title:	J. Org. Chem.
Volume:	77
Number:	22
Page Range:	S. 10145 - 10158
Date:	2012
Publisher:	AMER CHEMICAL SOC
Place of Publication:	WASHINGTON
ISSN:	1520-6904
Language:	English
Faculty:	Unspecified
Divisions:	Unspecified
Subjects:	no entry
Uncontrolled Keywords:	Keywords Language DERIVATIVES; ALCOHOLS; RECOGNITION; EPOXIDATION; ACTIVATION; ALDEHYDES; REAGENTS; SOLVENTS; ANALOGS; TADDOLS Multiple languages Chemistry, Organic Multiple languages
URI:	http://kups.ub.uni-koeln.de/id/eprint/47886