Phosphine ligands for catalytic reactions

Patent metadata

Field	Value
Publication number	US-9669399-B2
Application number	US-201615164002-A
Country	US
Kind code	B2
Filing date	May 25, 2016
Priority date	Jul 16, 2010
Publication date	Jun 6, 2017
Grant date	Jun 6, 2017

Abstract

The disclosure is directed to: (a) phosphacycle ligands; (b) catalyst compositions comprising phosphacycle ligands; and (c) methods of using such phosphacycle ligands and catalyst compositions in bond forming reactions.

First claim

We claim:

1. A compound having a structure corresponding to formula (I), or a salt thereof,

wherein Ar 1 and Ar 2 are each independently aryl or heteroaryl, and wherein Ar 1 and Ar 2 are each independently optionally substituted with one or more R 1 and R 2 , respectively;
R 1 and R 2 are independently selected at each occurrence from the group consisting of hydrogen; amino; hydroxyl; cyano; halo; alkyl; alkenyl; alkynyl; haloalkyl; haloalkoxy; oxoalkyl; alkoxy; aryloxy; heteroaryloxy; arylamino; heteroarylamino; alkylamino; dialkylamino; cycloalkyl optionally substituted with alkyl, alkenyl, alkynyl, alkoxy, cyano, halo, haloalkyl or haloalkoxy; cycloalkyloxy optionally substituted with alkyl, alkenyl, alkynyl, alkoxy, cyano, halo, haloalkyl or haloalkoxy; 5- or 6-membered heteroaryl optionally substituted with alkyl, alkenyl, alkynyl, alkoxy, cyano, halo, haloalkyl or haloalkoxy; phenyl optionally substituted with alkyl, alkenyl, alkynyl, alkoxy, cyano, halo, haloalkyl or haloalkoxy; hydroxyalkyl; hydroxyalkoxy; alkoxyalkyl; aminoalkyl; N-alkylaminoalkyl; N,N-dialkylaminoalkyl; N,N,N-trialkylammoniumalkyl; L 1 C(O)—OR 1′ , L 1 P(O)—(OR 1′ ) 2 , or L 1 -S(O) 2 —OR 1′ , wherein L 1 is a bond or alkylene, and R 1′ is selected from the group consisting of hydrogen, alkyl and hydroxyalkyl; L 2 -O—C(O)—R 2′ , wherein L 2 is a bond or alkylene, and R 2 is alkyl or hydroxyalkyl; L 3 -C(O)—NR 3′ R 4′ , wherein L 3 is a bond or alkylene, and R 3′ and R 4′ are each independently selected from the group consisting of hydrogen, alkyl, and hydroxyalkyl; L 4 -NR 5′ C(O)—R 6′ , wherein L 4 is a bond or alkylene, R 5′ is hydrogen or alkyl, and R 6′ is alkyl or hydroxyalkyl; sulfamoyl; N-(alkyl)sulfamoyl; N,N-(dialkyl)sulfamoyl; sulfonamide; sulfate; alkylthio; thioalkyl; and a ring containing an alkylene or —O—(CH 2 ) m —O— formed by the joining together of any two R 1 or any two R 2 or an R 1 and an R 2 , wherein m is 1, 2, 3 or 4;
X is a phosphine of formula (Ia):

wherein ring A includes 0 to 9 ring atoms in addition to the phosphorus and 2 carbon ring atoms of formula (Ia), wherein said ring atoms are each independently selected from the group consisting of carbon, oxygen, nitrogen, phosphorus and sulfur; and
wherein the ring atoms of ring A are each independently optionally substituted with one or more substituents selected from the group consisting of alkenyl; alkoxy; alkoxyalkyl; alkyl; alkylamino; alkylthio; alkynyl; aminoalkyl; N-alkylaminoalkyl; N,N-dialkylaminoalkyl; N,N,N-trialkylammoniumalkyl; arylalkyl optionally substituted with alkyl, alkenyl, alkynyl, alkoxy, cyano, halo, haloalkyl or haloalkoxy; cycloalkyl optionally substituted with alkyl, alkenyl, alkynyl, alkoxy, cyano, halo, haloalkyl or haloalkoxy; dialkylamino; halo; haloalkyl; fluoroalkyl; heteroaryl optionally substituted with alkyl, alkenyl, alkynyl, alkoxy, cyano, halo, haloalkyl or haloalkoxy; heterocycloalkyl optionally substituted with alkyl, alkenyl, alkynyl, alkoxy, cyano, halo, haloalkyl or haloalkoxy; hydroxy; hydroxyalkyl; oxo; an exocyclic double bond optionally substituted with alkyl, alkenyl, alkynyl, aryl, cycloalkyl, heterocyclyl, or heteroaryl; a 3- to 7-membered spiro ring containing zero, one, or two heteroatoms; phenyl optionally substituted with alkyl, alkenyl, alkynyl, alkoxy, cyano, halo, haloalkyl or haloalkoxy; L 1 -C(O)—OR″, L 1 -P(O)—(OR 1′ ) 2 , or L 1 S(O) 2 —OR 1′ , wherein L 1 is a bond or alkylene, and R 1′ is selected from the group consisting of hydrogen, alkyl or hydroxyalkyl; L 2 -O—C(O)—R 2′ , wherein L 2 is a bond or alkylene, and R 2′ is alkyl or hydroxyalkyl; L 3 -C(O)—NR 3′ R 4′ , wherein L 3 is a bond or alkylene, and R 3′ and R 4′ are each independently selected from the group consisting of hydrogen, alkyl, and hydroxyalkyl; L 4 -NR 5′ C(O)—R 6′ , wherein L 4 is a bond or alkylene, R 5′ is hydrogen or alkyl, and R 6′ is alkyl or hydroxyalkyl; and L 7 -NR 8′ —S(O) 2 —R 9′ , wherein L 7 is a bond or alkylene, R 8′ is hydrogen or alkyl, and R 9′ is alkyl or hydroxyalkyl; and
as to R 10 , R 11 , R 12 , and R 13 ,
i. R 10 or R 11 together with R 12 or R 13 form a ring; or
ii. R 10 and R 11 together with the carbon atom to which they are attached form a spirocyclic ring and/or R 12 and R 13 together with the carbon atom to which they are attached form a spirocyclic ring;
wherein, any of substituents R 10 , R 11 , R 12 , and R 13 that do not form the ring set forth in (i) or (ii) are each independently selected from the group consisting of hydrogen; alkyl; alkenyl; haloalkyl; alkynyl; oxoalkyl; cycloalkyl optionally substituted with alkyl, alkenyl, alkynyl, alkoxy, cyano, halo, haloalkyl or haloalkoxy; heterocyclyl optionally substituted with alkyl, alkenyl, alkynyl, alkoxy, cyano, halo, haloalkyl or haloalkoxy; heteroaryl optionally substituted with alkyl, alkenyl, alkynyl, alkoxy, cyano, halo, haloalkyl or haloalkoxy; phenyl optionally substituted with alkyl, alkenyl, alkynyl, alkoxy, cyano, halo, haloalkyl or haloalkoxy; hydroxyalkyl; alkoxyalkyl; aminoalkyl; N-alkylaminoalkyl; N,N-dialkylaminoalkyl; N,N,N-trialkylammoniumalkyl; thioalkyl; L 13 -C(O)—OR 14′ , L 13 -P(O)—(OR 14 ) 2 , or L 13 -S(O) 2 —OR 14 ″, wherein L 13 is a bond or alkylene, and R 14′ is selected from the group consisting of hydrogen, alkyl and hydroxyalkyl; L 15 -O—C(O)—R 16′ , wherein L 15 is alkylene and R 16′ is alkyl or hydroxyalkyl; L 17 -C(O)—NR 18′ R 19′ , wherein L 17 is a bond or alkylene, and R 18 and R 19′ are each independently selected from the group consisting of hydrogen, alkyl, and hydroxyalkyl; and L 20 -NR 2 ″—C(O)—R 22′ , wherein L 20 is alkylene, R 2 ″ is hydrogen or alkyl, and R 22′ is alkyl or hydroxyalkyl.

2. The compound or salt of claim 1 , wherein the compound has a structure corresponding to a structure of a formula selected from the group consisting of formulae (I-1)-(I-42):

wherein
V 1 , V 2 , V 3 , and V 4 are each independently CR 1 or N;
V 5 , V 6 , V 7 , V 8 and V 9 are each independently CR 2 or N;
W 1 , W 2 , an W 3 are each independently selected from the group consisting of CR 1 , NR 1 , N and O;
W 4 is C or N;
W 5 is C or N;
W 6 , W 7 , W 8 and W 9 are each independently selected from the group consisting of CR 2 , NR 2 , N and O; and
ring C, at each occurrence, is a fused-aryl or fused-heteroaryl and is optionally substituted with R 1 and R 2 .

3. The compound or salt of claim 1 , wherein the X is attached to an atom of Ar 1 adjacent to the atom bonded to Ar 2 .

4. The compound or salt of claim 1 , wherein Ar 1 and Ar 2 are each aryl.

5. The compound or salt of claim 1 , wherein Ar 2 is substituted with three R 2 .

6. The compound or salt of claim 1 , wherein R 2 is alkyl.

7. The compound or salt of claim 1 , wherein R 2 is isopropyl.

8. The compound or salt of claim 1 , wherein X is

Assignees

• Abbvie Inc

Inventors

• Shekhar Shashank
• Franczyk Thaddeus S
• Barnes David M
• Dunn Travis B
• Haight Anthony R
• Chan Vincent S

Classifications

• B01J2531/0205

  Bi- or polynuclear complexes, i.e. comprising two or more metal coordination centres, without metal-metal bonds, e.g. Cp(Lx)Zr-imidazole-Zr(Lx)Cp · CPC title

• B01J31/189

  containing both nitrogen and phosphorus as complexing atoms, including e.g. phosphino moieties, in one at least bidentate or bridging ligand · CPC title

• B01J31/2438

  and further hetero atoms as ring members, excluding the positions adjacent to P · CPC title

• B01J2540/40

  Non-coordinating groups comprising nitrogen · CPC title

• C07F9/509

  by reduction of pentavalent phosphorus derivatives, e.g. -P=X with X = O, S, Se or -P-Hal2 · CPC title