Phosphoramidite ligands in iridium-catalyzed allylic substitution
2006
Abstract
A new phosphoramidite ligand was used in the iridium-catalyzed allylic substitution reaction. This permitted high regio- and enantioselectivity on a wide variety of substrates and nucleophiles. Because of the stereospecificity of the reaction obtained by using branched substrates, a kinetic resoln. reaction was attempted. The origin of the impressive efficiency of this ligand in terms of kinetics was explored in detail, as was the role of the substituent in the ortho-position of the amine moiety. [on SciFinder (R)]
Details
Title
Phosphoramidite ligands in iridium-catalyzed allylic substitution
Author(s)
Polet, Damien ; Alexakis, Alexandre ; Tissot-Croset, Karine ; Corminboeuf, Clemence ; Ditrich, Klaus
Published in
Chemistry - A European Journal
Volume
12
Issue
13
Pages
3596-3609
Date
2006
ISSN
0947-6539
Keywords
Amination kinetics (iridium-catalyzed stereoselective allylic amination reaction using phosphoramidite derivs. as ligands); Density functional theory (iridium-catalyzed stereoselective allylic substitution reaction using chiral N; N-[(aryl)ethyl]dinaphtho[2; 1-d:1'; 2'-f][1; 3; 2]dioxaphosphepin-4-amine (phosphoramidite) ligand and related study of d. functional theory model); Amination (regioselective; iridium-catalyzed stereoselective allylic amination reaction using phosphoramidite derivs. as ligands); Amination; Amination catalysts (stereoselective; iridium-catalyzed stereoselective allylic amination reaction using phosphoramidite derivs. as ligands); iridium stereoselective allylic substitution phosphoramidite ligand; allylic substitution asym catalysis chiral ligand iridium phosphoramidite
Note
CAN 145:145318
25-7
Benzene, Its Derivatives, and Condensed Benzenoid Compounds
Department of Organic Chemistry,University of Geneva,Geneva,Switz.
Journal
written in English.
40032-55-1P; 86386-72-3P; 897963-63-2P Role: BYP (Byproduct), PREP (Preparation) (iridium-catalyzed stereoselective allylic amination reaction using phosphoramidite derivs. as ligands); 100-46-9 (Benzyl amine); 107-11-9 (Allylamine) Role: RCT (Reactant), RACT (Reactant or reagent) (iridium-catalyzed stereoselective allylic amination reaction using phosphoramidite derivs. as ligands); 111-26-2P (n-Hexylamine); 104937-80-6P; 223384-31-4P; 244221-60-1P; 735334-59-5P Role: SPN (Synthetic preparation), PREP (Preparation) (iridium-catalyzed stereoselective allylic amination reaction using phosphoramidite derivs. as ligands); 776316-53-1 Role: CAT (Catalyst use), USES (Uses) (iridium-catalyzed stereoselective allylic substitution reaction using chiral N,N-[(aryl)ethyl]dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-amine (phosphoramidite) derivs. as ligands); 209482-27-9P ((11bS)-N,N-Bis[(1S)-1-phenylethyl]dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-amine); 342813-26-7P; 776316-48-4P; 850796-15-5P; 850796-17-7P; 850797-26-1P; 898262-64-1P; 898262-65-2P Role: CAT (Catalyst use), SPN (Synthetic preparation), PREP (Preparation), USES (Uses) (iridium-catalyzed stereoselective allylic substitution reaction using chiral N,N-[(aryl)ethyl]dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-amine (phosphoramidite) derivs. as ligands); 850796-16-6P Role: CAT (Catalyst use), PRP (Properties), SPN (Synthetic preparation), PREP (Preparation), USES (Uses) (iridium-catalyzed stereoselective allylic substitution reaction using chiral N,N-[(aryl)ethyl]dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-amine (phosphoramidite) ligand and related study of d. functional theory model); 81586-82-5P; 119793-72-5P; 496789-07-2P; 685139-88-2P; 897963-53-0P Role: BYP (Byproduct), PREP (Preparation) (iridium-catalyzed stereoselective allylic substitution reaction using chiral phosphoramidite derivs. as ligands); 886759-00-8 Role: CAT (Catalyst use), USES (Uses) (iridium-catalyzed stereoselective allylic substitution reaction using chiral phosphoramidite derivs. as ligands); 105-45-3; 609-02-9; 2049-80-1; 2497-18-9; 7217-71-2 (alpha-Ethenylbenzenemethanol acetate); 18424-76-5; 21040-45-9; 41302-34-5; 85217-69-2; 107574-36-7; 170938-16-6; 373362-32-4; 496789-05-0; 496789-06-1; 512789-12-7; 897963-49-4; 897963-50-7; 897963-51-8 Role: RCT (Reactant), RACT (Reactant or reagent) (iridium-catalyzed stereoselective allylic substitution reaction using chiral phosphoramidite derivs. as ligands); 897963-57-4P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (iridium-catalyzed stereoselective allylic substitution reaction using chiral phosphoramidite derivs. as ligands); 92747-24-5P; 129101-14-0P; 164527-50-8P; 164713-27-3P; 189884-47-7P; 189884-50-2P; 776296-25-4P; 776296-26-5P; 776296-27-6P; 776296-28-7P; 776296-29-8P; 897963-54-1P; 897963-55-2P; 898262-66-3P Role: SPN (Synthetic preparation), PREP (Preparation) (iridium-catalyzed stereoselective allylic substitution reaction using chiral phosphoramidite derivs. as ligands); 12112-67-3 (Di-micro -chlorobis[(1,2,5,6-eta)-1,5-cyclooctadiene]diiridium) Role: CAT (Catalyst use), USES (Uses) (iridium-catalyzed stereoselective allylic substitution reaction using phosphoramidite derivs. as ligands); 73930-97-9 Role: RCT (Reactant), RACT (Reactant or reagent) (iridium-catalyzed stereoselective allylic substitution reaction using phosphoramidite derivs. as ligands); 87751-69-7P; 96482-64-3P Role: SPN (Synthetic preparation), PREP (Preparation) (iridium-catalyzed stereoselective allylic substitution reaction using phosphoramidite derivs. as ligands); 865-34-9 (Lithium methoxide) Role: RGT (Reagent), RACT (Reactant or reagent) (lithium methoxide as additive in iridium-catalyzed stereoselective allylic substitution reaction using phosphoramidite derivs. as ligands); 811803-79-9P; 897963-59-6P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of (phenyl)-3-cyclopentene-1,1-dicarboxylic acid di Et ester and related kinetic resoln. study); 98-86-2 (Acetophenone); 100-06-1 (1-(4-Methoxyphenyl)ethanone); 577-16-2 (1-(2-Methylphenyl)ethanone); 579-74-8 (1-(2-Methoxyphenyl)ethanone); 941-98-0 (1-(1-Naphthalenyl)ethanone); 2627-86-3; 5379-16-8; 10420-89-0; 18531-99-2 ((S)-BINOL); 20050-17-3; 41851-59-6; 68285-24-5; 76279-30-6 Role: RCT (Reactant), RACT (Reactant or reagent) (prepn. of chiral N,N-[(aryl)ethyl]dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-amine (phosphoramidite) derivs.); 90933-74-7P; 222180-06-5P; 676567-87-6P; 850790-52-2P; 850790-53-3P; 850790-54-4P; 897963-64-3P; 897963-65-4P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. of chiral N,N-[(aryl)ethyl]dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-amine (phosphoramidite) derivs.); 129646-79-3P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of alpha-(ethenyl)benzenemethanol acetate)
25-7
Benzene, Its Derivatives, and Condensed Benzenoid Compounds
Department of Organic Chemistry,University of Geneva,Geneva,Switz.
Journal
written in English.
40032-55-1P; 86386-72-3P; 897963-63-2P Role: BYP (Byproduct), PREP (Preparation) (iridium-catalyzed stereoselective allylic amination reaction using phosphoramidite derivs. as ligands); 100-46-9 (Benzyl amine); 107-11-9 (Allylamine) Role: RCT (Reactant), RACT (Reactant or reagent) (iridium-catalyzed stereoselective allylic amination reaction using phosphoramidite derivs. as ligands); 111-26-2P (n-Hexylamine); 104937-80-6P; 223384-31-4P; 244221-60-1P; 735334-59-5P Role: SPN (Synthetic preparation), PREP (Preparation) (iridium-catalyzed stereoselective allylic amination reaction using phosphoramidite derivs. as ligands); 776316-53-1 Role: CAT (Catalyst use), USES (Uses) (iridium-catalyzed stereoselective allylic substitution reaction using chiral N,N-[(aryl)ethyl]dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-amine (phosphoramidite) derivs. as ligands); 209482-27-9P ((11bS)-N,N-Bis[(1S)-1-phenylethyl]dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-amine); 342813-26-7P; 776316-48-4P; 850796-15-5P; 850796-17-7P; 850797-26-1P; 898262-64-1P; 898262-65-2P Role: CAT (Catalyst use), SPN (Synthetic preparation), PREP (Preparation), USES (Uses) (iridium-catalyzed stereoselective allylic substitution reaction using chiral N,N-[(aryl)ethyl]dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-amine (phosphoramidite) derivs. as ligands); 850796-16-6P Role: CAT (Catalyst use), PRP (Properties), SPN (Synthetic preparation), PREP (Preparation), USES (Uses) (iridium-catalyzed stereoselective allylic substitution reaction using chiral N,N-[(aryl)ethyl]dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-amine (phosphoramidite) ligand and related study of d. functional theory model); 81586-82-5P; 119793-72-5P; 496789-07-2P; 685139-88-2P; 897963-53-0P Role: BYP (Byproduct), PREP (Preparation) (iridium-catalyzed stereoselective allylic substitution reaction using chiral phosphoramidite derivs. as ligands); 886759-00-8 Role: CAT (Catalyst use), USES (Uses) (iridium-catalyzed stereoselective allylic substitution reaction using chiral phosphoramidite derivs. as ligands); 105-45-3; 609-02-9; 2049-80-1; 2497-18-9; 7217-71-2 (alpha-Ethenylbenzenemethanol acetate); 18424-76-5; 21040-45-9; 41302-34-5; 85217-69-2; 107574-36-7; 170938-16-6; 373362-32-4; 496789-05-0; 496789-06-1; 512789-12-7; 897963-49-4; 897963-50-7; 897963-51-8 Role: RCT (Reactant), RACT (Reactant or reagent) (iridium-catalyzed stereoselective allylic substitution reaction using chiral phosphoramidite derivs. as ligands); 897963-57-4P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (iridium-catalyzed stereoselective allylic substitution reaction using chiral phosphoramidite derivs. as ligands); 92747-24-5P; 129101-14-0P; 164527-50-8P; 164713-27-3P; 189884-47-7P; 189884-50-2P; 776296-25-4P; 776296-26-5P; 776296-27-6P; 776296-28-7P; 776296-29-8P; 897963-54-1P; 897963-55-2P; 898262-66-3P Role: SPN (Synthetic preparation), PREP (Preparation) (iridium-catalyzed stereoselective allylic substitution reaction using chiral phosphoramidite derivs. as ligands); 12112-67-3 (Di-micro -chlorobis[(1,2,5,6-eta)-1,5-cyclooctadiene]diiridium) Role: CAT (Catalyst use), USES (Uses) (iridium-catalyzed stereoselective allylic substitution reaction using phosphoramidite derivs. as ligands); 73930-97-9 Role: RCT (Reactant), RACT (Reactant or reagent) (iridium-catalyzed stereoselective allylic substitution reaction using phosphoramidite derivs. as ligands); 87751-69-7P; 96482-64-3P Role: SPN (Synthetic preparation), PREP (Preparation) (iridium-catalyzed stereoselective allylic substitution reaction using phosphoramidite derivs. as ligands); 865-34-9 (Lithium methoxide) Role: RGT (Reagent), RACT (Reactant or reagent) (lithium methoxide as additive in iridium-catalyzed stereoselective allylic substitution reaction using phosphoramidite derivs. as ligands); 811803-79-9P; 897963-59-6P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of (phenyl)-3-cyclopentene-1,1-dicarboxylic acid di Et ester and related kinetic resoln. study); 98-86-2 (Acetophenone); 100-06-1 (1-(4-Methoxyphenyl)ethanone); 577-16-2 (1-(2-Methylphenyl)ethanone); 579-74-8 (1-(2-Methoxyphenyl)ethanone); 941-98-0 (1-(1-Naphthalenyl)ethanone); 2627-86-3; 5379-16-8; 10420-89-0; 18531-99-2 ((S)-BINOL); 20050-17-3; 41851-59-6; 68285-24-5; 76279-30-6 Role: RCT (Reactant), RACT (Reactant or reagent) (prepn. of chiral N,N-[(aryl)ethyl]dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-amine (phosphoramidite) derivs.); 90933-74-7P; 222180-06-5P; 676567-87-6P; 850790-52-2P; 850790-53-3P; 850790-54-4P; 897963-64-3P; 897963-65-4P Role: RCT (Reactant), SPN (Synthetic preparation), PREP (Preparation), RACT (Reactant or reagent) (prepn. of chiral N,N-[(aryl)ethyl]dinaphtho[2,1-d:1',2'-f][1,3,2]dioxaphosphepin-4-amine (phosphoramidite) derivs.); 129646-79-3P Role: SPN (Synthetic preparation), PREP (Preparation) (prepn. of alpha-(ethenyl)benzenemethanol acetate)
Laboratories
LCMD
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Scientific production and competences > SB - School of Basic Sciences > ISIC - Institute of Chemical Sciences and Engineering > LCMD - Laboratory of Computational Molecular Design
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Published
Peer-reviewed publications
Work outside EPFL
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Record creation date
2007-10-22