Guanidinium compounds
The present application provides, inter alia, chemical compounds useful as synthesis intermediates, said compounds comprising one or more guanidinium moieties and a hypervalent iodine atom. Methods for making these compounds are also provided.
1. A compound of formula (I):
wherein:
G is -L-NH—C(—NH 2 )(═NH 2 )Y;
R is independently selected from the group consisting of halogen, C 1 -C 6 alkyl and C 1 -C 6 alkyloxy;
X is optionally substituted aryl;
Y is absent or is an anion selected from the group consisting of bicarbonate, halide, aryl carboxylate, alkyl carboxylate, phosphate, phosphonate, phosphonite, azide, thiocyanate, cyanate, phenoxide, arylsulfonate, alkylsulfonate, trifluoromethanesulfonate, thiolate, and stabilized enolate;
L is absent or is an optionally substituted linker selected from the group consisting of alkyl, alkenyl, heteroalkyl, alkylcarbonyl, heteroalkylcarbonyl, cycloalkyl, heterocycloalkyl, or aryl;
n is 0-4; and
m is 1-2.
2. The compound of claim 1 , wherein m is 1 and the compound of formula (I) has the structure of formula (II):
3. The compound of claim 1 , wherein X is aryl.
4. The compound of claim 1 , wherein the X is 4-methoxyphenyl.
5. The compound of claim 1 , wherein Y is trifluoromethylsulfonate.
6. The compound of claim 2 having the structure of formula (III):
7. The compound of claim 6 , having the structure of formula (IV):
8. The compound of claim 7 , having the structure of formula (V):
9. The compound of claim 6 , wherein X is aryl.
10. The compound of claim 6 , wherein X is 4-methoxyphenyl.
11. The compound of claim 6 , wherein each instance of Y is trifluoromethanesulfonyl.
12. The compound of claim 1 , wherein X is 4-methoxyphenyl and each instance of Y is trifluoromethanesulfonyl.
13. A method of making a compound of formula (I):
wherein:
G is -L-NH—C(—NH 2 )(═NH 2 )Y;
R is independently selected from the group consisting of halogen, C 1 -C 6 alkyl and C 1 -C 6 alkyloxy;
X is optionally substituted aryl;
Y is absent or is an anion selected from the group consisting of bicarbonate, halide, aryl carboxylate, alkyl carboxylate, phosphate, phosphonate, phosphonite, azide, thiocyanate, cyanate, phenoxide, arylsulfonate, alkylsulfonate, trifluoromethanesulfonate, thiolate, and stabilized enolate;
L is absent or is an optionally substituted linker selected from the group consisting of alkyl, alkenyl, heteroalkyl, alkylcarbonyl, heteroalkylcarbonyl, cycloalkyl, heterocycloalkyl, and aryl;
n is 0-4; and
m is 1-2;
the method comprising the steps of:
(1) reacting a compound of formula (Ia):
wherein G′ is -L-NH—C(—NH 2 )(═NH) or a salt thereof; and R is independently selected from the group consisting of halogen, C 1 -C 6 alkyl and C 1 -C 6 alkyloxy;
with a compound selected from the group consisting of (1-chloromethyl-4-fluoro-1,4-diazoniabicyclo[2.2.2]octane) bis(tetrafluoroborate), (1-fluoro-4-methyl-1,4-diazoniabicyclo[2.2.2]octane) bis(tetrafluoroborate), and optionally substituted N-fluoropyridinium tetrafluoroborate; and
a compound of formula:
wherein R 3 , R 4 and R 5 are optionally substituted substituents independently selected from the group consisting of alkyl, heteroalkyl, alkylaryl, aryl and heteroaryl; and
wherein Y is an anion selected from the group consisting of halide, aryl carboxylate, alkyl carboxylate, phosphate, phosphonate, phosphonite, azide, thiocyanate, cyanate, phenoxide, arylsulfonate, alkylsulfonate, trifluoromethanesulfonate, thiolate, and stabilized enolate;
to obtain a compound of formula (Ib):
and
(2) reacting the compound of formula (Ib) with a compound of formula:
X-M 1
wherein X is selected from the group consisting of optionally substituted aryl, optionally substituted heteroaryl, and stabilized enolate; and
M 1 is a borate, stannane, silane, or zinc moiety;
to obtain a compound of formula (I).
14. The compound of claim 1 having the structure:
15. A compound of formula (I):
wherein:
G is -L-NH—C(—NH 2 )(═NH 2 )Y;
R is independently selected from the group consisting of halogen, C 1 -C 6 alkyl and C 1 -C 6 alkyloxy;
X is optionally substituted heteroaryl;
Y is absent or is an anion selected from the group consisting of bicarbonate, halide, aryl carboxylate, alkyl carboxylate, phosphate, phosphonate, phosphonite, azide, thiocyanate, cyanate, phenoxide, arylsulfonate, alkylsulfonate, trifluoromethanesulfonate, thiolate, and stabilized enolate;
L is absent or is an optionally substituted linker selected from the group consisting of alkyl, alkenyl, heteroalkyl, alkylcarbonyl, heteroalkylcarbonyl, cycloalkyl, heterocycloalkyl, or aryl;
n is 0-4; and
m is 1-2.