# US 11,028,105 B2 · Difluoromethyl and difluoromethylene transfer reagents

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- Number: US 11,028,105 B2
- Document ID: US11028105B2
- Status: Granted
- Kind: B2
- Application number: 16/455,887
- Filed: 2019-06-28
- Published: 2020-01-02
- Granted: 2021-06-08
- Earliest claimed: 2018-06-29
- Assignees: The Regents of the University of Michigan
- Applicants: Regents of the University of Michigan
- Inventors: Nathaniel Szymczak; Jacob Geri
- Web page: https://patentgrep.com/patent/US11028105B2

## CPC

- C07F 5/05: Cyclic compounds having at least one ring containing boron but no carbon in the ring
- C07F 5/02: Boron compounds
- C07F 5/027: {Organoboranes and organoborohydrides}
- C07F 5/04: Esters of boric acids
- C07F: ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM (metal-containing porphyrins C07D487/22)

## Abstract

Disclosed herein are borazine, borate, and azaborinine compounds and compositions, methods of making said compounds and compositions, and methods of forming aromatic difluorocarbon compounds and difluorocarbon compounds.

## Claims

### Claim 1

A compound of Formula (I):
having a structure of:
wherein:
the dashed lines indicate optional double bonds;
R1 is C6-20 aryl or C1-15 heteroaryl, and the heteroaryl comprises 1-5 ring heteroatoms selected from N, O, and S;
each R2 and R3 is independently OH, N(R4)2, C1-6 alkyl, C3-8cycloalkyl, OC1-6 alkyl, or OC3-8 cycloalkyl; or adjacent R2 and R3, taken together with the atoms to which they are attached, form an optionally substituted 5-7 membered ring;
each R4 is independently C1-6 alkyl or C3-8cycloalkyl;
each R5 is independently C1-6 alkyl, C3-8cycloalkyl; or
each R5 taken together with the atoms to which they are attached form an optionally substituted 5-7 membered ring;
each R6 is independently C1-6 alkyl, C3-8cycloalkyl, OC1-6 alkyl, or OC3-8cycloalkyl; and
M comprises a counterion.

### Claim 2 (depends on 1)

The compound of claim 1, wherein R1 is C6-20aryl.

### Claim 3 (depends on 1)

The compound of claim 1, wherein R1 is C1-15heteroaryl.

### Claim 4 (depends on 1)

The compound of claim 1, wherein R1 is selected from the group consisting of:
and
X is H, F, Cl, Br, I, CHs, OH, NH2, NO2, C1-4 alkyl, OC1-4 alkyl, CO2H, CHO, CF3, or CN.

### Claim 5 (depends on 1)

The compound of claim 1, wherein at least one R2 or R3 is methyl.

### Claim 6 (depends on 1)

The compound of claim 1 having a structure selected from the group consisting of:

### Claim 7 (depends on 1)

A composition comprising the compound of claim 1 and a crown ether.

### Claim 8 (depends on 1)

A method for preparing the compound of claim 1, comprising contacting H—CF2R1 with a Lewis acid, a base, and optionally a crown ether under conditions sufficient to form the compound, wherein the Lewis acid has a structure:

### Claim 9 (depends on 8)

The method of claim 8, wherein the H—CF2R1 is selected from the group consisting of:
and
X is H, F, Cl, Br, I, CHs, OH, NH2, NO2, C1-4alkyl, OC1-4alkyl, CO2H, CHO, CF3, or CN.

### Claim 10 (depends on 1)

A method of forming an aromatic difluorocarbon compound comprising admixing the compound of claim 1, with an electrophile under conditions sufficient to couple the electrophile and CF2R1 to form the aromatic difluorocarbon compound.

### Claim 11

A compound of Formula (III)
wherein:
the dashed lines indicate optional double bonds;
R1 is H, C6-20aryl, or C1-15heteroaryl, and the heteroaryl comprises 1-5 ring heteroatoms selected from N, O, and S;
R2 and R3 are independently OH, N(R4)2, C1-6alkyl, C3-8cycloalkyl, OC1-6 alkyl, or OC3-8 cycloalkyl, or R2 and R3, taken together with the atoms to which they are attached, form an optionally substituted 5-7 membered ring;
each R4 is independently C1-5alkyl or C3-8cycloalkyl;
each R7 is independently H, C1-6 alkyl, C3-8cycloalkyl, or at least one adjacent R7 pair, taken together with the atoms to which they are attached, form an optionally substituted 5-7 membered ring; and
M comprises a counterion.

### Claim 12 (depends on 11)

The compound of claim 11, selected from the group consisting of:

### Claim 13 (depends on 11)

The compound of claim 11, wherein R1 is H.

### Claim 14 (depends on 11)

The compound of claim 11, wherein R1 is C6-20 aryl.

### Claim 15 (depends on 11)

The compound of claim 11, wherein R1 is C1-15 heteroaryl.

### Claim 16 (depends on 11)

The compound of claim 11, wherein R1 is selected from the group consisting of:
and
X is H, F, Cl, Br, I, CH3, OH, NH2, NO2, C1-4 alkyl, OC1-4 alkyl, CO2H, CHO, CF3, or CN.

### Claim 17 (depends on 11)

The compound of claim 11, wherein at least one of R2 and R3 is methyl.

### Claim 18 (depends on 11)

A composition comprising the compound of claim 11 and a crown ether.

### Claim 19 (depends on 11)

A method for preparing the compound of claim 11, comprising contacting H—CF2R1 with a Lewis acid, a base, and optionally a crown ether under conditions sufficient to form the compound, wherein the Lewis acid has a structure:

### Claim 20 (depends on 11)

A method of forming a difluorocarbon compound comprising admixing the compound of, claim 11, with an electrophile under conditions sufficient to couple the electrophile and CF2R1 to form the aromatic difluorocarbon compound.