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US 2024/0165597 A1Published application
Sterically hindered n-aliphatic n-heterocyclic carbene catalysts and methods using same
AssigneeRutgers, The State University of New Jersey
InventorsMichal Szostak, Md. Mahbubur Rahman
Life of this patent
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Abstract
The present disclosure relates in part to sterically hindered N-aliphatic N-heterocyclic carbene (NHC) ligands, which are readily synthetically available from inexpensive starting materials. The present disclosure further relates to NHC catalyst complexes comprising transition metals such as Cu, Ag, Au, and Pd. Furthermore, the present disclosure provides methods for using the catalysts described herein in a number of organic transformations, including alkyne hydroboration and hydration, in addition to C—O, C—C, and C—N coupling reactions.
Claims29
A compound of formula (I):
- wherein:
- X is a counter anion;
- R1 and R2 are each independently selected from the group consisting of H, optionally substituted C1-C6 alkyl, optionally substituted C2-C6 alkenyl, optionally substituted benzyl, optionally substituted phenyl, and optionally substituted naphthyl, and optionally substituted C4-C10 heteroaryl, or
- R1 and R2 may combine with the ring to which they are attached to form C5-C12 cycloalkyl, C6-C10 aryl, or C4-C10 heteroaryl,
- wherein each optional substituent in R1 and R2 is independently at least one substituent selected from the group consisting of C1-C3 alkyl, C2-C6 alkenyl, phenyl, naphthyl, C4-C10 heteroaryl, N(Ra)(Rb), ORb, CN, CF3, OCF3, C(═O)Rb, N(R)S(═O)2Rb, C(═O)N(Ra)(Rb), and C(═O)ORb;
- R3 and R4 are each independently
- R5 and R5′ are each independently selected from the group consisting of C1-C6 alkyl, C3-C12 cycloalkyl, C2-C10 heterocycloalkyl, C6-C10 aryl, C4-C10 heteroaryl, halogen, ORb, N(Ra)(Rb), SRb, and Si(Rb)3,
- wherein R5 and R5′ may combine with the carbon atom to which they are bound to form one selected from the group consisting of C3-C8 cycloalkyl and C2-C7 heterocycloalkyl;
- R6, R6′, and R6″ are each independently selected from the group consisting of H, C1-C6 alkyl, C3-C12 cycloalkyl, C2-C10 heterocycloalkyl, C6-C10 aryl, C4-C10 heteroaryl, halogen, ORb, N(Ra)(Rb), SRb, and Si(Rb)3,
- wherein at least two of R6, R6′, and R6″ may combine with the carbon atom to which they are bound to form one selected from the group consisting of C3-C12 cycloalkyl, C2-C10 heterocycloalkyl, C5-C12 fused cycloalkyl, C4-C10 fused heterocycloalkyl, C5-C12 bridged cycloalkyl, and C4-C10 bridged heterocycloalkyl,
- wherein any one of R6, R6′, and R6″ may combine with any one of R5 and R5′ and the carbon atoms to which they are bound to form one selected from the group consisting of C4-C12 cycloalkyl and C3-C10 heterocycloalkyl, and
- wherein if R5 and R5′ are Me, and two of R6, R6′, and R6″ are H, then the other one of R6, R6′, and R6″ is not H or Me;
- wherein if R5 and R5′ are Me, two of R6, R6′, and R6″ are H, and one of R6, R6′, and R6″ is t-Bu, then M is not BF4;
- bond a is a single or double bond;
- each occurrence of Ra is independently H or C1-C3 alkyl;
- each occurrence of Rb is independently selected from the group consisting of H, C1-C6 alkyl, C1-C3 haloalkyl, C2-C6 alkenyl, benzyl, naphthyl, C4-C10 heteroaryl, and phenyl optionally substituted with at least one substituent selected from the group consisting of C1-C3 alkyl and halogen;
- and
- m is 1 or 2.
15 more elements
4-11. (canceled)
A compound of formula (II):
- wherein:
- M is a transition metal;
- L is a ligand of M, wherein each occurrence of L can be the same or different;
- R1 and R2 are each independently selected from the group consisting of H, optionally substituted C1-C6 alkyl, optionally substituted C2-C6 alkenyl, optionally substituted benzyl, optionally substituted phenyl, and optionally substituted naphthyl, and optionally substituted C4-C10 heteroaryl, or
- R1 and R2 may combine with the ring to which they are attached to form C5-C12 cycloalkyl, C6-C10 aryl, or C4-C10 heteroaryl,
- wherein each optional substituent in R1 and R2 is independently at least one substituent selected from the group consisting of C1-C3 alkyl, C2-C6 alkenyl, phenyl, naphthyl, C4-C10 heteroaryl, N(Ra)(Rb), ORb, CN, CF3, OCF3, C(═O)Rb, N(R)S(═O)2Rb, C(═O)N(Ra)(Rb), and C(═O)ORb;
- R3 and R4 are each independently
- R5 and R5′ are each independently selected from the group consisting of C1-C6 alkyl, C3-C12 cycloalkyl, C2-C10 heterocycloalkyl, C6-C10 aryl, C4-C10 heteroaryl, halogen, ORb, N(Ra)(Rb), SRb, and Si(Rb)3,
- wherein R5 and R5′ may combine with the carbon atom to which they are bound to form one selected from the group consisting of C3-C8 cycloalkyl and C2-C7 heterocycloalkyl;
- R6, R6′, and R6″ are each independently selected from the group consisting of H, C1-C6 alkyl, C3-C12 cycloalkyl, C2-C10 heterocycloalkyl, C6-C10 aryl, C4-C10 heteroaryl, halogen, ORb, N(Ra)(Rb), SRb, and Si(Rb)3,
- wherein at least two of R6, R6′, and R6″ may combine with carbon atom to which they are bound to form one selected from the group consisting of C3-C12 cycloalkyl, C2-C10 heterocycloalkyl, C5-C12 fused cycloalkyl, C4-C10 fused heterocycloalkyl, C5-C12 bridged cycloalkyl, and C4-C10 bridged heterocycloalkyl,
- wherein any one of R6, R6′, and R6″ may combine with any one of R5 and R5′ and the carbon atoms to which they are bound to form one selected from the group consisting of C4-C12 cycloalkyl and C3-C10 heterocycloalkyl, and
- wherein if R5 and R5′ are Me, and two of R6, R6′, and R6″ are H, then the other one of R6, R6′, and R6″ is not H or Me;
- each occurrence of is a single or double bond,
- wherein no more than one bonding a C atom and a N atom is a double bond;
- each occurrence of Ra is independently H or C1-C3 alkyl;
- each occurrence of Rb is independently selected from the group consisting of H, C1-C6 alkyl, C1-C3 haloalkyl, C2-C6 alkenyl, benzyl, naphthyl, C4-C10 heteroaryl, and phenyl optionally substituted with at least one substituent selected from the group consisting of C1-C3 alkyl and halogen;
- n is an integer which is selected from the group consisting of 1, 2, 3, 4, and 5;
- and
- m is an integer which is either 1 or 2.
17 more elements
(canceled)
18-27. (canceled)
31-32. (canceled)
35-40. (canceled)
43-50. (canceled)
53-58. (canceled)
61-65. (canceled)
67-68. (canceled)
Dependencies are inferred from the claim text.