Manganese (III) catalyzed C—H aminations

Patent metadata

Field	Value
Publication number	US-10611786-B2
Application number	US-201816153178-A
Country	US
Kind code	B2
Filing date	Oct 5, 2018
Priority date	Oct 9, 2017
Publication date	Apr 7, 2020
Grant date	Apr 7, 2020

Abstract

Reactions that directly install nitrogen into C—H bonds of complex molecules are significant because of their potential to change the chemical and biological properties of a given compound. Selective intramolecular C—H amination reactions that achieve high levels of reactivity, while maintaining excellent site-selectivity and functional-group tolerance is a challenging problem. Herein is reported a manganese perchlorophthalocyanine catalyst [Mn III (ClPc)] for intermolecular benzylic C—H amination of bioactive molecules and natural products that proceeds with unprecedented levels of reactivity and site-selectivity. In the presence of Brønsted or Lewis acid, the [Mn III (ClPc)]-catalyzed C—H amination demonstrates unique tolerance for tertiary amine, pyridine and benzimidazole functionalities. Mechanistic studies indicate that C—H amination proceeds through an electrophilic metallonitrene intermediate via a stepwise pathway where C—H cleavage is the rate-determining step of the reaction. Collectively these mechanistic features contrast previous base-metal catalyzed C—H aminations. The catalyst can be a compound of Formula I:

First claim

What is claimed is:

1. A compound of Formula I:

wherein
X is an anion;
each R 1 is independently chloro, bromo, iodo, —C(═O)R 2 , —S(═O) 2 R 3 , —C≡CR 4 , —CQ 3 , or —CQ 2 CQ 3 ;
R 2 is H, —CQ 3 , —(C 1 -C 6 )alkyl, OR 5 , N(R 5 ) 2 , or phenyl;
R 3 is —CQ 3 , —(C 1 -C 6 )alkyl, N(R 5 ) 2 , or phenyl;
R 4 is H, halo, —CQ 3 , —(C 1 -C 6 )alkyl, or phenyl;
Q is choro or fluoro;
each R 5 is independently H, or —(C 1 -C 6 )alkyl;
n is 3 or 4; and
the oxidation state of Mn is +3;

wherein optionally each phenyl is independently substituted with 1-5 substituents.

2. The compound of claim 1 wherein:
each R 1 is independently chloro, bromo, —C(═O)R 2 , —S(═O) 2 R 3 , —CQ 3 , or —CQ 2 CQ.

3. The compound of claim 1 wherein X is halo or SbF 6 .

4. The compound of claim 1 wherein R 1 is chloro.

5. The compound of claim 1 wherein the compound of Formula I is a compound of Formula II:

wherein X is Cl or SbF 6 .

6. A composition comprising a compound of claim 1 and a salt.

7. The composition of claim 6 wherein the salt is AgSbF 6 .

8. The composition of claim 6 wherein the compound is 3:

Assignees

• Univ Illinois

Inventors

• White M Christina
• Clark Joseph R
• Feng Kaibo
• Sookezian Anasheh
• Wendell Chloe

Classifications

• C07D493/22

  in which the condensed system contains four or more hetero rings · CPC title

• C07D307/87

  Benzo [c] furans; Hydrogenated benzo [c] furans · CPC title

• C07D211/28

  to which a second hetero atom is attached · CPC title

• C07D221/20

  Spiro-condensed ring systems · CPC title

• C07D221/10

  Aza-phenanthrenes · CPC title