Catalytic carbonylation catalysts and methods

A catalyst comprising:

• i) a metal complex of formula:
• wherein:
• M is a metal atom;
• a is an integer from 1 to 4 inclusive;
• at least on of R1a, R1a′, R2a, R2a′, R3a, R3a′, Rc, and Rd is independently (Z+)b, wherein:
• is a bond or a linker;
• Z+comprises an atom selected from the group consisting of nitrogen, phosphorous, arsenic, and sulfur;
• and
• b is an integer from 1 to 4 inclusive;
• the remaining R1a, R1a′, R2a, R2a′, R3a′ at each occurrence are independently hydrogen, halogen, —OR4, —NRy2, —CN, —NO2, —SO2Ry, —SO2NRy2, —CNO, —NCO, or —N3;
• or an optionally substituted group selected from the group consisting of:
• C1-20 aliphatic;
• C1-20 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;
• wherein:
• R4 at each occurrence is a hydroxyl protecting group or Ry;
• Ry at each occurrence is independently hydrogen, or an optionally substituted group selected from the group consisting of:
• acyl;
• carbamoyl;
• arylalkyl;
• 6- to 10-membered aryl;
• C1-12 aliphatic;
• C1-12 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;
• or
• wherein two Ryon the same nitrogen atom are 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;
• wherein any of (R2a′ and R3a′), (R2a and R3a), (R1a and R2a), and (R1a′ and R2a′) may optionally be taken together with the carbon atoms to;
• which they are attached to form one or more rings:
• R4a is selected from the group consisting of
• wherein:
• Rd at each occurrence is independently (Z+)b, hydrogen, halogen, —OR4, —NRy2, —CN, —NO2, —SO2Ry, —SORy, —SO2NRy2, —CNO, —NCO, or —N3;
• or an optionally substituted group selected from the group consisting of:
• C1-20 aliphatic;
• C1-20 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 the group consisting of nitrogen, oxygen, and sulfur;
• and
• 4- to 7-membered heterocyclic having 1-2 heteroatoms independently selected from the group consisting of nitrogen, oxygen, and sulfur, or
• wherein two or more Rd groups are taken together to form one or more optionally substituted rings;
• Rc at each occurrence is independently (Z+)b, hydrogen, halogen, —NRy2, —SRy, —CN, —NO2,—SO2Ry, —SORy, —SO2NRy2, —CNO, —NCO, or —N3;
• or an optionally substituted group selected from the group consisting of:
• C1-20 aliphatic;
• C1-20 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;
• or
• wherein two or more Rc groups are taken together with the carbon atoms to which they are attached and any intervening atoms to form one or more rings;
• or
• wherein two Rc groups are attached to the same carbon atom, and are taken together along with the carbon atom to which they are attached to form a moiety selected from the group consisting of:
• a 3- to 8-membered spirocyclic ring;
• a carbonyl;
• an oxime;
• a hydrazine;
• and
• an imine:
• m′ is 0 or an integer from 1 to 4, inclusive;
• and
• q is 0 or an integer from 1 to 4, inclusive;
• and
• ii) at least one anionic metal carbonyl species associated with at least one of Z+.