Synthesis of cyclophanes from a self-assembly reaction

Patent metadata

Field	Value
Publication number	US-9790192-B2
Application number	US-201514944584-A
Country	US
Kind code	B2
Filing date	Nov 18, 2015
Priority date	Nov 18, 2014
Publication date	Oct 17, 2017
Grant date	Oct 17, 2017

Abstract

Disclosed herein is a novel method for preparing cyclophanes, comprising forming a disulfide cyclophane by contacting a linker moiety which includes two or more thiol groups, with a metal salt and an oxidant. The disulfide cyclophane is then desulfurized to form a thiacyclophane comprising thioether bridges. This thiacyclophane optionally may be further desulfurized to form an unsaturated hydrocarbon cyclophane, which can then be reduced to form a saturated hydrocarbon cyclophane. The various cyclophanes can be synthesized in a ring form, such as a dimer, trimer or tetramer etc., or they can be synthesized in a tetrahedral or larger structure. Also disclosed are novel cyclophanes formed by the disclosed method.

First claim

We claim:

1. A compound, having a formula

wherein:
ring 1 is aryl or heteroaryl;
each R independently is carboxyl ester, aminocarbonyl, aliphatic, heteroaliphatic, NO 2 , sulfonyl, amine, protected amine, aryl, heteroaryl, OH, oxo or halogen;
m independently is from 0 to 4;
p is from 1 to 10;
each L independently is aliphatic, aralkyl, aryl, heteroaryl or heteroaralkyl; and
if the compound has formula I, ring 1 is 1,4-disubstituted phenyl, m is 0 and each L is CH 2 , then p is not 1, 2 or 3;
if the compound has formula I, ring 1 is 1,3-disubstituted phenyl, m is 0 and each L is CH 2 , then p is not 1; and
if the compound has formula I, ring 1 is 1,5-naphthyl, m is 0 and each L is CH 2 , then p is not 1.

2. The compound of claim 1 , wherein the compound has a formula

3. The compound of claim 1 , wherein m is greater than 0.

4. The compound of claim 1 , wherein each R independently is heteroaliphatic.

5. The compound of claim 4 , wherein each R is methoxy.

6. The compound of claim 1 , wherein each L independently is aliphatic or aralkyl.

7. The compound of claim 6 , wherein at least one L is CH 2 .

8. The compound of claim 1 , wherein ring 1 is phenyl, naphthyl or biphenyl.

9. The compound of claim 1 , wherein the

moiety is selected from

each R a independently is hydrogen, carboxyl ester, aminocarbonyl, aliphatic, heteroaliphatic, NO 2 , sulfonyl, amine, protected amine, aryl, heteroaryl, OH or halogen;
each R b independently is hydrogen, aliphatic or heteroaliphatic;
each R c independently is hydrogen, aliphatic or heteroaliphatic; and
q is from 1 to 4.

10. The compound of claim 9 , wherein each R b and R c is hydrogen.

11. The compound of claim 9 , wherein each R a is hydrogen or alkoxy.

12. The compound of claim 1 , wherein the compound has a formula

13. The compound of claim 12 , wherein the compound has a formula

14. A compound selected from

15. The compound of claim 1 , wherein p is greater than 3.

16. The compound of claim 6 , wherein at least one L is benzyl.

Assignees

• Univ Oregon

Inventors

• Johnson Darren W
• Collins Mary

Classifications

• C07D251/24 Primary

  to three ring carbon atoms · CPC title

• C07D341/00

  Heterocyclic compounds containing rings having three or more sulfur atoms as the only ring hetero atoms · CPC title

• C07C321/16

  of a saturated carbon skeleton containing rings · CPC title

• C07D495/22

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