Synthesis of metal complexes and uses thereof
The present disclosure provides novel methods of making aluminum complexes with utility for promoting epoxide carbonylation reactions. Methods include reacting neutral metal carbonyl compounds with alkylaluminum complexes. For example, a compound of formula I: is reacted with a neutral metal carbonyl compound (such as Q′ d M e (CO) w′ ) to produce an aluminum-based carbonylation catalyst:
1. A method for preparing an aluminum-based carbonylation catalyst and a ketone, the method comprising reacting a compound of formula I with a neutral metal carbonyl compound to produce an aluminum-based carbonylation catalyst and a ketone, wherein:
the compound of formula I is
the neutral metal carbonyl compound is Co 2 (CO) 8 ;
the aluminum-based carbonylation catalyst is
the ketone is
wherein:
Q is a nitrogen atom and the four Q groups are part of a single porphyrin ligand; and
R q is alkyl.
2. The method of claim 1 , wherein the moiety
is:
wherein:
R d is independently at each occurrence hydrogen, halogen, —OR 4 , —NR y 2 , —SR, —CN, —NO 2 , —SO 2 R y , —SOR y , —SO 2 NR y 2 ; —CNO, —NRSO 2 R y , —NCO, —N 3 , —SiR 3 ; or an optionally substituted group selected from the group consisting of C 1-20 aliphatic; C 1-20 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6- to 10-membered aryl; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur, where two or more R d groups may be taken together to form one or more optionally substituted rings,
each R y is independently hydrogen, or an optionally substituted group selected from the group consisting of: carbamoyl, arylalkyl; 6- to 10-membered aryl; C 1-12 aliphatic; C 1-12 heteroaliphatic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; an oxygen protecting group; and a nitrogen protecting group; where two R y on the same nitrogen atom may be taken with the nitrogen atom to form an optionally substituted 4- to 7-membered heterocyclic ring having 0-2 additional heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur,
R 4 is a hydroxyl protecting group or R y , and
R is independently at each occurrence optionally substituted C 1-12 aliphatic or optionally substituted aryl.
3. The method of claim 1 , wherein the moiety
is selected from the group consisting of:
4. The method of claim 1 , wherein the moiety
is:
wherein:
R d is independently at each occurrence hydrogen, halogen, —OR 4 , —NR y 2 , —SR, —CN, —NO 2 , —SO 2 R y , —SOR y , —SO 2 NR y 2 ; —CNO, —NRSO 2 R y , —NCO, —N 3 , —SiR 3 ; or an optionally substituted group selected from the group consisting of C 1-20 aliphatic; C 1-20 heteroaliphatic having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 6- to 10-membered aryl; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur; and 4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur, where two or more R d groups may be taken together to form one or more optionally substituted rings,
each R y is independently hydrogen, or an optionally substituted group selected from the group consisting of: carbamoyl, arylalkyl; 6- to 10-membered aryl; C 1-12 aliphatic; C 1-12 heteroaliphatic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 5- to 10-membered heteroaryl having 1-4 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; 4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur; an oxygen protecting group; and a nitrogen protecting group; where two R y on the same nitrogen atom may be taken with the nitrogen atom to form an optionally substituted 4- to 7-membered heterocyclic ring having 0-2 additional heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur,
R 4 is a hydroxyl protecting group or R y , and
R is independently at each occurrence optionally substituted C 1-12 aliphatic or optionally substituted aryl.
5. The method of claim 1 , wherein the moiety
is:
6. The method of claim 1 , wherein the moiety
is selected from the group consisting of:
7. The method of claim 1 , wherein the carbonylation catalyst is produced in a composition having a halide or alkali metal salt content in an amount less than about 200 ppm.
8. The method of claim 1 , wherein R q is a C 1-12 alkyl group.
9. The method of claim 1 , wherein R q is selected from the group consisting of methyl, ethyl, n-propyl, i-propyl, n-butyl, i-butyl, and octyl.
10. The method of claim 1 , wherein R q is ethyl.
11. The method of claim 1 , wherein the compound of formula I is: