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Towards enantiopure macrocyclic trans-dinucleating hemilabile P-Alkene ligands: Syntheses, structures, and Chiral Pd-Complexes


Frieß, Sibylle; Herrera, Alberto; Linden, Anthony; Heinemann, Frank W; Dorta, Romano (2019). Towards enantiopure macrocyclic trans-dinucleating hemilabile P-Alkene ligands: Syntheses, structures, and Chiral Pd-Complexes. Journal of Organometallic Chemistry, 898:120876.

Abstract

Dibenzazepinyl dichlorophosphine 2 reacts with (R,R)-2,3-O-isopropylidene-threitol (3) in $Et2_O$ solution to afford gram-quantities of the enantiopure macrocylic phosphoramidite (all-R)-6, which may be seen as a formal dimer of classic phosphoramidite P-alkene hybrid ligands. Complexation experiments with $PdCl_2$ reveal highly selective formation of the trans-dinuclear complex (all-R)-11. The corresponding bulkier and rigidly trans-eclipsed 1,4-diol (S,S)-bis-hydroximethyl-9,10- dihydro-9,10-ethaneanthracene (4), does not favor macrocycle formation and exclusively leads to the new dibenzazepinyl phsophormaidite P-alkene ligand 7, which in Pd-catalyzed asymmetric allylic amination comes the well-known ‘privileged’ binol-derived P-alkene analogue 1 close in terms of enantioselection.

Abstract

Dibenzazepinyl dichlorophosphine 2 reacts with (R,R)-2,3-O-isopropylidene-threitol (3) in $Et2_O$ solution to afford gram-quantities of the enantiopure macrocylic phosphoramidite (all-R)-6, which may be seen as a formal dimer of classic phosphoramidite P-alkene hybrid ligands. Complexation experiments with $PdCl_2$ reveal highly selective formation of the trans-dinuclear complex (all-R)-11. The corresponding bulkier and rigidly trans-eclipsed 1,4-diol (S,S)-bis-hydroximethyl-9,10- dihydro-9,10-ethaneanthracene (4), does not favor macrocycle formation and exclusively leads to the new dibenzazepinyl phsophormaidite P-alkene ligand 7, which in Pd-catalyzed asymmetric allylic amination comes the well-known ‘privileged’ binol-derived P-alkene analogue 1 close in terms of enantioselection.

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Additional indexing

Item Type:Journal Article, refereed, original work
Communities & Collections:07 Faculty of Science > Department of Chemistry
Dewey Decimal Classification:540 Chemistry
Uncontrolled Keywords:Physical and Theoretical Chemistry, Inorganic Chemistry, Organic Chemistry, Materials Chemistry, Biochemistry
Language:English
Date:1 October 2019
Deposited On:20 Nov 2019 15:12
Last Modified:21 Nov 2019 02:14
Publisher:Elsevier
ISSN:0022-328X
OA Status:Closed
Publisher DOI:https://doi.org/10.1016/j.jorganchem.2019.120876

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