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US 10,196,413 B2Granted
Chiral dihydrobenzoazaphosphole ligands and synthesis thereof
AssigneeBoehringer Ingelheim International GmbH
InventorsSoumik Biswas, Jean-Nicolas Desrosiers, Kendricks Lao, Hari P. R. Mangunuru, Bo Qu, Sonia Rodriguez, Chris Hugh Senanayake, Joshua Daniel Sieber, Xiao-Jun Wang, Nathan K. Yee, Yongda Zhang
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Abstract
This invention relates to novel phosphorous ligands useful for organic transformations. Methods of making and using the ligands in organic synthesis are described. The invention also relates to processes for preparing the novel ligands.
Claims10
A compound of formula I
- wherein each
- R1 is selected from H, C1-6alkyl, —C(O)C1-6alkyl, —C(O)NHR5, —SO2C1-6alkyl, —S(O)C1-6alkyl, —P(O)R13R14, —SiR13, —C(═NR13)NR13R14, optionally substituted benzyl and optionally substituted aryl or heteroaryl;
- R2 and R2′ are each independently selected from the group consisting of hydrogen, halo, perhaloalkyl, —NR11R12, —OR11, —SR11, —Si(R11)3, P(O)R13R14, —CN, —NO2, —OH, alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, arylalkyl, heteroarylalkyl, bicycloaryl, heterobicycloaryl, C(O)alkyl, —C(S)alkyl, —S(O)1-2alkyl, benzyl, aryl, heteroaryl, aryloxy and heteroaryloxy, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, benzyl, aryl and heteroaryl are unsubstituted or substituted;
- R3 is selected from alkyl, cycloalkyl or optionally substituted aryl;
- R4 is hydrogen, halo, perhaloalkyl, —NR11R12, —OR11, —SR11, —Si(R11)3, —CN, —NO2, —OH, alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, benzyl, aryl, alkyl, heteroarylalkyl, bicycloaryl, heterobicycloaryl, C(O)alkyl, —C(S)alkyl, —S(O)1-2alkyl, benzyl, aryl, heteroaryl, aryloxy and heteroaryloxy, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl are unsubstituted or substituted;
- or
- R4 is X—R6;
- or
- R4 is the group
- wherein * indicates the point of attachment;
- X is selected from O, NR10, CR11R12 and S;
- R5 is selected from C1-6alkyl and optionally substituted phenyl
- each R6, R7, R8 and R9 is independently selected from the group consisting of hydrogen, halo, perhaloalkyl, —NR11R12, —OR11, —SR11, —Si(R11)3, —CN, —NO2, —OH, alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, benzyl, aryl, alkyl, heteroarylalkyl, heterobicycloaryl, —C(O)alkyl, —C(S)alkyl, —S(O)1-2alkyl, benzyl, aryl, heteroaryl, aryloxy and heteroaryloxy, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl are unsubstituted or substituted;
- R10, R11 and R12 are independently selected from H, C1-6alkyl, C1-6alkenyl, C1-6alkynyl, perhaloC1-6alkyl, —C(O)C1-6alkyl, cycloalkyl, heterocyclyl, optionally substituted benzyl, optionally substituted aryl and optionally substituted heteroaryl;
- and
- R13 and R14 are independently selected from C1-6alkyl and optionally substituted aryl;
- and the diastereomers and enantiomers thereof.
14 more elements
A compound selected from the group consisting of
- and the enantiomers and diastereomers thereof.
A method for the synthesis of compound III comprising
- reacting intermediate Ma, wherein R′ and R are independently selected from C1-6alkyl and Prt is a protecting group with a suitable base to provide intermediate IIIb;
- and
- removing the protecting group to provide III.
A compound of formula II
- wherein
- R1 and R1′ are independently selected from —SO2aryl, —C(O)-aryl, —C(O)C1-6alkyl, —NC(O)-aryl and —NC(O)C1-6alkyl, wherein each aryl and alkyl is optionally substituted;
- R3 and R3′ are independently selected from alkyl, cycloalkyl and optionally substituted aryl;
- R4, R4′, R7, R7′, R8, R8′, R9 and R9′ are independently selected from hydrogen, halo, perhaloalkyl, —NR11R12, —OR11, —SR11, —Si(R11)3, —CN, —NO2, —OH, alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, benzyl, aryl, alkyl, heteroarylalkyl, bicycloaryl, heterobicycloaryl, —C(O)alkyl, —C(S)alkyl, —S(O)1-2alkyl, benzyl, aryl, heteroaryl, aryloxy and heteroaryloxy, wherein each alkyl, alkenyl, alkynyl, cycloalkyl, heterocycloalkyl, aryl and heteroaryl are unsubstituted or substituted;
- and
- R11 and R12 are independently selected from H, C1-6alkyl, C3-6cycloalkyl, CH2C3-10cycloalkyl, —C(O)C1-6alkyl, optionally substituted aryl, heteroaryl and —CH2-aryl;
- and
- and the diastereomers and enantiomers thereof.
5 more elements
Dependencies are inferred from the claim text.