Transition metal complex containing sulfonamide or amide group for olefin metathesis reaction and application thereof

Patent metadata

Field	Value
Publication number	US-10933409-B2
Application number	US-201716072192-A
Country	US
Kind code	B2
Filing date	Jan 25, 2017
Priority date	Feb 1, 2016
Publication date	Mar 2, 2021
Grant date	Mar 2, 2021

Abstract

Disclosed is a novel transition metal complex containing N-heterocyclic carbene and a sulfonamide group, or N-heterocyclic carbene and an amide group, and application thereof, the traquesnsition metal complex having a wider range of general purposes in olefin metathesis and being able to be variably controlled in reactivity.

First claim

The invention claimed is:

1. A transition metal complex, represented by the following Chemical Formula A:
(L1)M(B)(L2) n (L3) m   [Chemical Formula A]

wherein,
M is a transition metal of ruthenium,
L1 means a phosphine ligand or N-heterocyclic carbene ligand containing a substituted or unsubstituted alkyl of 1 to 30 carbon atoms or a substituted or unsubstituted aryl of 6 to 30 carbon atoms,
L2 and L3, which are the same or different, are each a monovalent ligand selected from among a hydrogen atom, a deuterium atom, a halogen, a cyano, a substituted or unsubstituted alkyl of 1 to 30 carbon atoms, a substituted or unsubstituted aryl of 6 to 50 carbon atoms, a substituted or unsubstituted arylalkyl of 7 to 50 carbon atoms, a substituted or unsubstituted alkenyl of 2 to 30 carbon atoms, a substituted or unsubstituted alkynyl of 2 to 20 carbon atoms, a substituted or unsubstituted cycloalkyl of 3 to 30 carbon atoms, a substituted or unsubstituted cycloalkenyl of 5 to 30 carbon atoms, a substituted or unsubstituted alkoxy of 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy of 6 to 30 carbon atoms, a substituted or unsubstituted arylthioxy of 6 to 30 carbon atoms, a substituted or unsubstituted alkylthioxy of 1 to 30 carbon atoms, a substituted or unsubstituted heteroaryl of 2 to 50 carbon atoms bearing O, N, or S as a heteroatom, a substituted or unsubstituted carboxylate anion of 1 to 30 carbon atoms, and a nitrate (NO3-); or
a neutral ligand selected from among a phosphine containing a substituted or unsubstituted alkyl of 1 to 30 carbon atoms or a substituted or unsubstituted aryl of 6 to 50 carbon atoms, carbon monoxide, an amine containing a substituted or unsubstituted alkyl of 1 to 30 carbon atoms or a substituted or unsubstituted aryl of 6 to 50 carbon atoms, a nitrile containing a substituted or unsubstituted alkyl of 1 to 30 carbon atoms or a substituted or unsubstituted aryl of 6 to 50 carbon atoms, and a substituted or unsubstituted aromatic heterocyclic compound of 2 to 50 carbon atoms bearing O, N, or S as a heteroatom;
in the alterative for L2 and L3, L2 and L3 are connected to each other to form a ring with M, and when L2 and L3 are each plural, the corresponding plural L2's or L3's are connected to each other to form a ring with M,
n and m, which are the same or different, are each independently an integer of 0 to 2 and when n or m is 2 or greater, the corresponding plural L2's or L3's are the same or different, and
A is a ligand represented by the following Structural Formula A-1 or A-2:

wherein,
R11 to R13, which are the same or different, are each independently selected from among a hydrogen atom, a deuterium atom, a substituted or unsubstituted alkyl of 1 to 30 carbon atoms, a substituted or unsubstituted 7 aryl of 6 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl of 3 to 30 carbon atoms, a substituted or unsubstituted heteroaryl of 2 to 50 carbon atoms bearing at least one selected from among O, N, S, and Si as a heteroatom, a substituted or unsubstituted alkoxy of 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy of 6 to 30 carbon atoms, a substituted or unsubstituted alkylamine of 1 to 30 carbon atoms, a substituted or unsubstituted aryl amine of 6 to 30 carbon atoms, a substituted or unsubstituted alkylsilyl of 1 to 30 carbon atoms, a substituted or unsubstituted arylsilyl of 6 to 30 carbon atoms, a cyano, and a halogen, and
‘..’ means a pair of electrons of carbene.

2. The transition metal complex of claim 1 , wherein L2 and L3, which are the same or different, are each independently a halogen selected from among F, Cl, Br and I, and n and m are each an integer of 1 in Chemical Formula A.

3. The transition metal complex of claim 1 , wherein the N-heterocyclic carbene ligand is represented by the following Chemical Formula B:

wherein
X1 is selected from among O, S, N-R2, C-R3, and C-R4R5,
a single or a double bond is between X1 and Y1, between Y1 and Y2, and between Y2 and Y3,
Y1 to Y3, which are the same or different, are each independently selected from among N, N-R6, C-R7, and C-R8R9,
m is an integer of 0 to 3, and when m is 2 or greater, the corresponding plural Y2's are the same or different, with a single or a double bond therebetween,
R1 to R9, which are the same or different, are each independently selected from among a hydrogen atom, a deuterium atom, a halogen, a substituted or unsubstituted alkyl of 1 to 30 carbon atoms, a substituted or unsubstituted aryl of 6 to 50 carbon atoms, a substituted or unsubstituted arylalkyl of 7 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl of 3 to 30 carbon atoms, a substituted or unsubstituted alkoxy of 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy of 6 to 30 carbon atoms, and a substituted or unsubstituted heteroaryl of 2 to 50 carbon atoms bearing O, N, or S as a heteroatom,
with a proviso that R1 and R2 are each neither a hydrogen atom nor a deuterium atom, and
‘..’ means a pair of electrons in carbene.

4. The transition metal complex of claim 3 , wherein the N-heterocyclic carbene ligand is one selected from among Chemical Formulas B-1 to B-13:

wherein R1 and R2 are each as defined above,
R′ is selected from among a hydrogen atom, a deuterium atom, a halogen, a substituted or unsubstituted alkyl of 1 to 30 carbon atoms, a substituted or unsubstituted aryl of 6 to 50 carbon atoms, a substituted or unsubstituted arylalkyl of 7 to 50 carbon atoms, a substituted or unsubstituted cycloalkyl of 3 to 30 carbon atoms, a substituted or unsubstituted alkoxy of 1 to 30 carbon atoms, a substituted or unsubstituted aryloxy of 6 to 30 carbon atoms, a substituted or unsubstituted heteroaryl of 2 to 50 carbon atoms bearing O, N, or S as a heteroatom,
n is an integer of 1 to 8, and
when plural R's exist in one molecule, R's are the same or different.

5. The transition metal complex of claim 4 , wherein the N-heterocyclic carbene is one selected from among the following Chemical Formulas B-20 to B-37:

6. The transition metal complex of claim 1 , wherein an oxygen atom and a carbon atom of the carbene moiety in Structural Formulas A-1 and A-2 are bound to the transition metal.

7. The transition metal complex of claim 1 , wherein at least one of the substituents R11 to R13 contains a fluorine atom.

8. A method for conducting an olefin metathesis reaction, comprising using the transition metal complex of claim 1 .

9. The method of claim 8 , wherein the metathesis reaction is a ring-closing metathesis reaction.

10. A catalyst for olefin metathesis, prepared by supporting the transition metal complex of claim 1 on a carrier.

Assignees

• Seoul Nat Univ R&Db Foundation

Inventors

• Hong Soon Hyeok
• Kim Gunsoon
• Song Gitaek

Classifications

• C07F15/06

  Cobalt compounds · CPC title

• C07C201/00

  Preparation of esters of nitric or nitrous acid or of compounds containing nitro or nitroso groups bound to a carbon skeleton · CPC title

• B01J31/16

  containing coordination complexes · CPC title

• B01J31/2226

  Anionic ligands, i.e. the overall ligand carries at least one formal negative charge · CPC title

• C07C67/333

  by isomerisation; by change of size of the carbon skeleton (introduction or elimination of carboxyl groups C07C67/313, C07C67/32) · CPC title