Methods for synthesizing vinylidenes and alkenes

1. A method for synthesizing a compound of Formula VI

the method comprising reacting a compound of Formula II

with a compound of Formula VII

or an acetal derivative or a polyacetal derivative thereof, at elevated temperature to form the compound of Formula VI;

wherein:

R 1 is selected from hydrogen, alkyl, cycloalkyl, heterocycle, aryl, heteroaryl, OR 3 , SR 3 , and NR 4 R 5 , each of which may be optionally substituted with one or more Z groups;

R 2 is NR 6 R 7 ;

R 3 is selected from alkyl, cycloalkyl, heterocycle, aryl, and heteroaryl, each of which may be optionally substituted with one or more Z groups;

R 4 and R 5 are independently selected from hydrogen, alkyl, cycloalkyl, heterocycle, aryl, and heteroaryl, each of which may be optionally substituted with one or more Z groups; or

R 4 and R 5 may be brought together with the nitrogen to which they are attached to form a heterocycle ring or a heteroaryl ring, wherein said heterocycle ring or heteroaryl ring may be optionally substituted with one or more Z groups;

R 6 and R 7 are independently selected hydrogen, alkyl, cycloalkyl, heterocycle, aryl, and heteroaryl, each of which may be optionally substituted with one or more Z groups; or

R 6 and R 7 may be brought together with the nitrogen to which they are attached to form a heterocycle ring or a heteroaryl ring, wherein said heterocycle ring or heteroaryl ring may be optionally substituted with one or more Z groups;

R 20 is selected from hydrogen, alkyl, cycloalkyl, heterocycle, aryl, and heteroaryl, each of which may be optionally substituted with one or more Z groups; and

Z is independently selected at each occurrence from alkyl, haloalkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocycle, aldehyde, amino, carboxylic acid, ester, ether, halo, hydroxy, keto, nitro, cyano, azido, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, sulfonylamino, and thiol.

2. The method of claim 1 , wherein the compound of Formula VII, or acetal derivative or polyacetal derivative thereof, is paraformaldehyde.

3. The method of claim 1 , wherein the compound of Formula VII, or acetal derivative or polyacetal derivative thereof, is dimethoxymethane.

4. The method of claim 1 , wherein the compound of Formula VII, or acetal derivative or polyacetal derivative thereof, is 1,3,5-trioxane.

5. The method of claim 1 , wherein the compound of Formula VII, or acetal derivative or polyacetal derivative thereof, is acetaldehyde.

6. The method of claim 1 , wherein the molar ratio of the compound of Formula VII, or acetal derivative or polyacetal derivative thereof, to the compound of Formula II is about 2:1, about 2.5:1, about 3:1, about 3.5:1, or about 4:1.

7. The method of claim 1 , wherein the compound of Formula II is reacted with the compound of Formula VII, or acetal derivative or polyacetal derivative thereof, at a temperature from about 50° C. to about 120° C.

8. The method of claim 1 , wherein the compound of Formula II is reacted with the compound of Formula VII, or acetal derivative or polyacetal derivative thereof, in the presence of a solvent.

9. The method of claim 8 , wherein the solvent is selected from pentane, cyclopentane, hexane, cyclohexane, benzene, carbon tetrachloride, toluene, 1,4-dioxane, diethyl ether, chloroform, dichloromethane, tetrahydrofuran, ethyl acetate, acetone, dimethylformamide, acetonitrile, dimethylsulfoxide, nitromethane, propylene carbonate, formic acid, n-butanol, isopropyl alcohol, n-propanol, ethanol, methanol, acetic acid, and water, or combinations thereof.

10. The method of claim 1 , wherein R 1 is NR 4 R 5 .

11. The method of claim 10 , wherein R 4 and R 5 are brought together with the nitrogen to which they are attached to form a heterocycle ring or a heteroaryl ring, each of which is optionally substituted with one or more Z groups.

12. The method of claim 1 , wherein R 1 is selected from

13. The method of claim 1 , wherein R 1 is selected from

14. The method of claim 1 , wherein R 6 and R 7 are brought together with the nitrogen to which they are attached to form a heterocycle ring or a heteroaryl ring, each of which is optionally substituted with one or more Z groups.

15. The method of claim 1 , wherein R 2 is selected from

16. The method of claim 1 , wherein R 2 is selected from

17. The method of claim 1 wherein the compound of Formula VI is selected from:

18. A compound of Formula I-a or Formula VI-a:

wherein:

X 1 , X 2 , X 3 , X 4 , X 5 , and X 6 are each selected from N, CH, or C—Z,

wherein at least one of X 1 , X 2 , X 3 , X 4 , X 5 , and X 6 is C—Z,

wherein no more than one of X 1 , X 2 , and X 3 is N;

wherein no more than one of X 4 , X 5 , and X 6 is N;

R 20 is selected from hydrogen, alkyl, cycloalkyl, heterocycle, aryl and heteroaryl, each of which may be optionally substituted with one or more Z groups; and

Z is independently selected at each occurrence from alkyl, haloalkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocycle, aldehyde, amino, carboxylic acid, ester, ether, halo, hydroxy, keto, nitro, cyano, azido, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, sulfonylamino, and thiol.

19. A compound of Formula III or Formula III-a

and one or more anions balancing the charge of the compound of Formula III or Formula III-a;

wherein:

R 10 and R 11 are independently selected from alkyl, cycloalkyl, aryl, or heteroaryl, each of which may be optionally substituted with one or more Z groups;

X 1 , X 2 , X 3 , X 4 , X 5 and X 6 are independently selected from N, C—H, or C—Z;

wherein no more than one of X 1 , X 2 , and X 3 are N;

wherein no more than one of X 4 , X 5 , and X 6 are N;

R 20 is selected from hydrogen, alkyl, cycloalkyl, heterocycle, aryl, and heteroaryl, each of which may be optionally substituted with one or more Z groups; and

Z is independently selected at each occurrence from alkyl, haloalkyl, alkoxy, alkenyl, alkynyl, aryl, heteroaryl, cycloalkyl, heterocycle, aldehyde, amino, carboxylic acid, ester, ether, halo, hydroxy, keto, nitro, cyano, azido, silyl, sulfo-oxo, sulfonyl, sulfone, sulfoxide, sulfonylamino, and thiol.

20. The compound of claim 19 selected from: