Enantiopure terphenyls with two ortho-atropisomeric axes

Patent metadata

Field	Value
Publication number	US-11434253-B2
Application number	US-201816772284-A
Country	US
Kind code	B2
Filing date	Dec 12, 2018
Priority date	Dec 14, 2017
Publication date	Sep 6, 2022
Grant date	Sep 6, 2022

Abstract

Enantiopure terphenyl presenting two ortho-located chiral axes having the following structural formula (I): their process of synthesis and their use as mono or bidentate ligands for asymmetric organometallic reactions, as organocatalysts, as chiral base and as generator, with metal, of isolable chiral metallic complexes for applications in asymmetric catalysis and others.

First claim

The invention claimed is:

1. Enantiopure terphenyl presenting two ortho-located chiral axis having the following structural formula (I)

wherein
R 1 on the phenyl ring Ar1 represents
a halogen atom, or
a substituted or unsubstituted branched or straight alkyl group, or
a substituted or unsubstituted cycloalkyl group, or
a substituted or unsubstituted branched or straight alkoxy group, or
a CH 2 F group, or a CHF 2 group or a —CnF n+2 group with n=1 to 10 or,
a substituted or unsubstituted aryl group or,
a —COR a or a —COOR a group with R a selected from a substituted or unsubstituted branched or straight alkyl group or a substituted or unsubstituted aryl group or
a —NR b R c group with R b and R c independently selected from a hydrogen atom, a substituted or unsubstituted branched or straight alkyl group or a substituted or unsubstituted aryl group or forming a NH 2 -protecting group, or
a BR a R b group with R a and R b , identical or different being as defined above or
a —B(OR d )(OR e ) group with R d and R e identical or different being selected from a hydrogen atom or a substituted or unsubstituted branched or straight alkyl group,

R 2 in position 4 or 5 of the phenyl ring Ar1 which bears it represents
a hydrogen atom or
a halogen atom,
a substituted or unsubstituted branched or straight alkyl group or
a substituted or unsubstituted cycloalkyl group, or
a substituted or unsubstituted branched or straight alkoxy group or
a substituted or unsubstituted aryl group or
a —COR a or a —COOR a group with R a selected from a substituted or unsubstituted branched or straight alkyl group or a substituted or unsubstituted aryl group, or
a —NR b R c group with R b and R c independently selected from a hydrogen atom, a substituted or unsubstituted branched or straight alkyl group, or a substituted or unsubstituted aryl group, or forming a NH 2 -protecting group or
a —BR a Rb group with R a and R b identical or different being as defined above or,
a —B(OR d )(OR e ) group with Rd and Re identical or different being selected from a hydrogen atom or a substituted or unsubstituted branched or straight alkyl group,

R 3 on the phenyl ring Ar1 represents
a halogen atom or
a substituted or unsubstituted branched or straight alkyl group or,
a substituted or unsubstituted cycloalkyl group, or
a substituted or unsubstituted branched or straight alkoxy group or
a substituted or unsubstituted aryl group or
a —COR a or a —COOR a group with R a selected from a substituted or unsubstituted branched or straight alkyl group or a substituted or unsubstituted aryl group, or
a —NR b R c group with R b and R c independently selected from a hydrogen atom, a substituted or unsubstituted branched or straight alkyl group, or a substituted or unsubstituted aryl group, or forming a NH 2 -protecting group,
a —BR a R b group with R a and R b identical or different being as defined above or,
a —B(OR d )(OR e ) group with R d and R e identical or different being selected from a hydrogen atom or a substituted or unsubstituted branched or straight alkyl group,

R 4 , which may be in position 2, 3, 4 or 5 on the phenyl ring Art which bears it, represents:
a hydrogen atom or
a halogen atom or
a substituted or unsubstituted branched or straight alkyl group or,
a substituted or unsubstituted cycloalkyl group, or
a CH 2 F group, or a CHF 2 group or —CnF n+2 group with n=1 to 10, or
a substituted or unsubstituted aryl group, or
a —OR a , a —COR a or a —COOR a group with R a selected from a substituted or unsubstituted branched or straight alkyl group or a substituted or unsubstituted aryl group, or
a —NR b R c group with R b and R c independently selected from a hydrogen atom, a substituted or unsubstituted branched or straight alkyl group, or a substituted or unsubstituted aryl group, or forming a NH 2 -protecting group, or
a —BR a R b group with R a and R b identical or different being as defined above or,
a —B(OR d )(OR e ) group with R d and R e identical or different being selected from a hydrogen atom or a substituted or unsubstituted branched or straight alkyl group,

R 5 on the phenyl ring Art represents a coordinating group or a substituent that will be used to install a coordinating group, selected from:
a halogen atom,
an —OR b group with Rb selected from a hydrogen atom, a substituted or unsubstituted branched or straight alkyl group, or a substituted or unsubstituted aryl group, or a NH 2 -protecting group or

a —CH 2 OR b group with R b selected from a hydrogen atom, a substituted or unsubstituted branched or straight alkyl group, or a substituted or unsubstituted aryl group, or
a —CHO group or
a —COOR b group with R b selected from a hydrogen atom, a substituted or unsubstituted branched or straight alkyl group, or a substituted or unsubstituted aryl group, or a NH 2 -protecting group, or
a —NR b R c group with R b and R c independently selected from a hydrogen atom, a substituted or unsubstituted branched or straight alkyl group, or a substituted or unsubstituted aryl group, or a NH 2 -protecting group,
a —SOR a group or a —SR a group or a —SO 2 R a with R a selected from a substituted or unsubstituted branched or straight alkyl group or a substituted or unsubstituted aryl group, or
a —PR a R d or a —P (O)R a n d with R a and R d independently selected from a substituted or unsubstituted branched or straight alkyl group or a substituted or unsubstituted aryl group, or
a —C═NR b with R b as defined above or
a substituted or unsubstituted oxazoline group or
a substituted or unsubstituted indenyl group or
a substituted or unsubstituted cyclopentadienyl group,

R 6 on the phenyl ring Ar3 is a coordinating group
either represents
a hydrogen atom or
a halogen atom,
an —OH group
a substituted or unsubstituted branched or straight alkyl group or
a substituted or unsubstituted cycloalkyl group, or
a substituted or unsubstituted aryl group or
a —SOR a group or a —SR a group or a —SO 2 R a with R a selected from a substituted or unsubstituted branched or straight alkyl group or a substituted or unsubstituted aryl group, or
a —OR a , a —COR a or a —COOR a group with R a selected from a substituted or unsubstituted branched or straight alkyl group or a substituted or unsubstituted aryl group, or
a —NR b R c group with R b and R c independently selected from a hydrogen atom, a substituted or unsubstituted branched or straight alkyl group, or a substituted or unsubstituted aryl group, or forming a NH 2 -protecting group or,
a —BR a R b group with R a and R b identical or different being as defined above or,
a —B(OR d )(OR e ) group with R d and R e identical or different being selected from a hydrogen atom or a substituted or unsubstituted branched or straight alkyl group,
a —PR a R d or a —P (O)R a R d with R a and R d independently selected from a substituted or unsubstituted branched or straight alkyl group or a substituted or unsubstituted aryl group, or
a substituted or unsubstituted or oxazoline group
a substituted or unsubstituted indenyl group or
a substituted or unsubstituted cyclopentadienyl group,

or may form with R 5
a bridged phosphoric acid or ester or phosphinate represented by formula

with X being a carbon or an oxygen atom and Ra selected from a hydrogen atom or a substituted or unsubstituted branched or straight alkyl group; or
a bridged phosphoramidite or phosphoramine represented by formula

Assignees

• Univ Strasbourg
• Centre Nat Rech Scient

Inventors

• Dherbassy Quentin
• Wencel-Delord Joanna
• Colobert Françoise
• Hedouin Gaspard

Classifications

• B01J2531/822

  Rhodium · CPC title

• C07C65/24

  polycyclic · CPC title

• C07B53/00 Primary

  Asymmetric syntheses · CPC title

• B01J2231/643

  of R2C=O or R2C=NR (R= C, H) · CPC title

• C07C313/00

  Sulfinic acids; Sulfenic acids; Halides, esters or anhydrides thereof; Amides of sulfinic or sulfenic acids, i.e. compounds having singly-bound oxygen atoms of sulfinic or sulfenic groups replaced by nitrogen atoms, not being part of nitro or nitroso groups · CPC title