Spiro-1,1'-bindane-7,7-bisphosphine oxides as highly active supporting ligands for paladium-catalyzed asymmetric heck reaction

Patent metadata

Field	Value
Publication number	US-2016136629-A1
Application number	US-201414896289-A
Country	US
Kind code	A1
Filing date	Jun 5, 2014
Priority date	Jun 5, 2013
Publication date	May 19, 2016
Grant date	—

Abstract

The present invention relates to catalyst complexes comprising palladium (Pd) and at least one spiro-1,1′-biindane-7,7′-bisphosphine oxide ligand as disclosed herein, and their use. The present invention is further directed to the asymmetric catalyzed covalent carbon-carbon single bond formation from aryl, heteroaryl and alkenyl triflates and halides and olefins utilising the said catalyst complexes.

First claim

1 . Catalyst complex comprising Pd and at least one ligand of Formula (I)

wherein,
R′ and R″ are independently selected from the group consisting of substituted or unsubstituted, linear or branched alkyl with 1 to 20 carbon atoms; substituted or unsubstituted, linear or branched alkenyl with 2 to 20 carbon atoms; substituted or unsubstituted cycloalkyl with 5 to 20 carbon atoms; substituted or unsubstituted cycloalkenyl with 5 to 20 carbon atoms; substituted or unsubstituted aryl with 5 to 14 carbon atoms; and substituted or unsubstituted heteroaryl with 5 to 14 carbon atoms.

2 . Catalyst complex according to claim 1 , wherein the ligand of Formula (I) is a ligand of Formula (II) or Formula (III)

wherein,
R′ and R″ are independently selected from the group consisting of substituted or unsubstituted, linear or branched alkyl with 1 to 20 carbon atoms; substituted or unsubstituted, linear or branched alkenyl with 2 to 20 carbon atoms; substituted or unsubstituted cycloalkyl with 5 to 20 carbon atoms; substituted or unsubstituted cycloalkenyl with 5 to 20 carbon atoms; substituted or unsubstituted aryl with 5 to 14 carbon atoms; and substituted or unsubstituted heteroaryl with 5 to 14 carbon atoms.

3 . Catalyst complex according to claim 1 or 2 , wherein R′ and R″ are independently selected from the group consisting of cyclohexanyl (Cy), phenyl (Ph), 1,3-dimethylbenzene (meta-Xylyl), and para-FC 6 H 4 .

4 . Catalyst complex according to any of claim 1 or 3 , wherein the ligand is independently selected from the group consisting of

and mixtures thereof.

5 . Catalyst complex according to any of claims 1 to 4 , wherein the Pd is a Pd(0) and/or a Pd(+II) specie.

6 . Catalyst complex according to any of claims 1 to 5 , wherein the Pd is a Pd(0) specie.

7 . Catalyst complex according to any of claims 1 to 6 , wherein the Pd(0) specie is generated in situ.

8 . Catalyst complex according to any of claims 1 to 7 , wherein the Pd is generated from a Pd precursor selected from the group consisting of Pd(dba) 2 , Pd 2 (dba) 3 , Pd(PPh 3 ) 4 , Pd(OAc) 2 , PdCl 2 , PdBr 2 , PdI 2 , PdCl 2 (PPh 3 ) 2 , Pd(OAc) 2 , Pd(Ptert-butyl 3 ) 2 , or a mixture thereof.

9 . Catalyst complex according to any of claims 1 to 8 , wherein the Pd precursor is selected from the group consisting of Pd(OAc) 2 , Pd(dba) 2 , or Pd 2 (dba) 3 .

10 . Method for forming a covalent carbon-carbon single bond in the Pd-catalyzed Heck carbon-carbon coupling reaction, the method comprising:
providing the catalyst complex according to any of claims 1 to 9 ; and (ii) reacting at least one electrophilic compound of the Formula (IV) with at least one olefin of the Formula (V)

wherein
R 1 is any organic compound;
R 2 and R 3 combine to form together with the carbon atoms to which they are attached a substituted or unsubstituted 5- to 40-membered cycloalkenyl or heterocycloalkenyl; and
LG' and LG 2 are leaving groups; and
in the presence of the catalyst complex under conditions suitable for forming the covalent carbon-carbon single bond.

11 . Method according to claim 10 , wherein the organic moiety is independently selected from the group consisting of linear or branched, substituted or unsubstituted C 1 -C x alkyl; linear or branched, substituted or unsubstituted alkenyl with 2 to x carbon atoms; linear or branched, substituted or unsubstituted alkynyl with 2 to x carbon atoms; linear or branched, substituted or unsubstituted alkoxy with 1 to x carbon atoms; substituted or unsubstituted cycloalkyl with 3 to x carbon atoms; substituted or unsubstituted cycloalkenyl with 3 to x carbon atoms; substituted or unsubstituted aryl with 6 to x carbon atoms; and substituted or unsubstituted heteroaryl with 3 to x carbon atoms; with x being any integer of 2 or more, preferably up to 50, more preferably up to 30.

12 . Method according to claim 10 or 11 , wherein R 1 is selected from the group consisting of linear or branched, substituted or unsubstituted alkenyl with 2 to x carbon atoms; substituted or unsubstituted cycloalkenyl with 3 to x carbon atoms; substituted or unsubstituted cycloalkenyl with 3 to x carbon atoms; substituted or unsubstituted aryl with 6 to x carbon atoms; and substituted or unsubstituted heteroaryl with 3 to x carbon atoms; with x being any integer of 2 or more, preferably up to 50, more preferably up to 30.

13 . Method according to any one of claims 10 to 12 , wherein R 1 is selected from the group consisting of substituted or unsubstituted, linear or branched alkenyl with 3 to 15 carbon atoms; substituted or unsubstituted benzene; and substituted or unsubstituted naphthalene.

14 . Method according to any one of claims 10 to 13 , wherein LG 1 is selected from the group consisting of halogen, —OSO 2 C 4 F 9 , —OSO 2 CF 3 , —OSO 2 F, —OTs, and —OMs.

15 . Method according to any one of claims 10 to 14 , wherein LG 1 is selected from the group consisting of Cl, Br, I, and —OSO 2 CF 3 .

16 . Method according to any one of claims 10 to 15 , LG 1 is —OSO 2 CF 3 or Br.

17 . Method according to any one of claims 10 to 16 , wherein the at least one electrophilic compound of Formula (IV) is selected from the group consisting 1-bromonaphthalene, 2-bromonaphthalene, bromobenzene, 4-bromoanisole, 4-bromotoluene, 1-bromo-4-fluorobenzene, 2-bromoanisole, N-methyl-2-bromopyrrole, 3-bromoindole, 5-bromo-2-methyl-1,3-benzothiazole, 3-bromobenzofuran, 3-bromobenzothiophene, 2-bromothiophene, 2-bromothiophene, 4-bromo-3-chromene, 1-bromostyrene and (E)-2-bromostyrene, 1-bromocyclohexene, 1-bromocyclopentene, bromoethene, (E)-1-bromopropene, 2-bromopropene, iodobenzene, 1-iodonaphthalene, 2-iodonaphthalene, 4-iodoanisole, 4-iodotoluene, 4-chlorotoluene, 2-chlorotoluene, 1-chloronaphthalene, 2-chloronaphthalene, chlorobenzene, 4-chloroanisole, 2-chioroanisole, 3-chloroindole, N-methyl-2-chloropyrrole, 5-chloro-1,3-benzothiazole, 3-chlorobenzofuran, 3-chlorobenzothiophene, 2-chlorothiophene, 2-chlorothiophene, 1-naphthyl triflate, 2-naphthyl triflate, phenyl triflate, para-tert-butylphenyl triflate, para-(trifluoromethyl)phenyl triflate, para-chlorophenyl triflate, and para-fluorophenyl triflate, para-formylphenyl triflate, para-(ethoxycarbonyl)phenyl triflate, para-anisyl triflate, para-tert-butylphenyl triflate, ortho-methyiphenyl triflate, para-chlorophenyl triflate, para-benzophenonyl triflate, ortho-anisyl triflate, meta-anisyl triflate, 1-tosyl-1H-indol-5-yl triflate, 2-methylbenzo[d]thiazol-5-yl triflate, 2-thienyl and 3-thienyl trilfates and their benzo-derivatives, 2-furanyl and 3-furanyl triflates and their benzo-derivatives, N-Boc-2-pyrrolidinyl and N-Boc-3-pyrrolidinyl trilfates, cyclohexenyl triflate, 2-methylcyclohexenyl triflate, 1-styryl and (E)-2-styryl trilfates.

18 . Method according to any one of claims 10 to 17 , wherein R 2 and R 3 combine to form together with the carbon atoms to which they are attached a substituted or unsubstituted 5- to 20-membered cycloalkenyl or heterocycloalkenyl.

19 . Method according to any one of claims 10 to 18 , wherein R 2 and R 3 combine to form to

Assignees

• Univ Nanyang Tech

Inventors

• Zhou Jianrong Steve
• Hu Jian
• Wu Chunlin

Classifications

• C07B37/04

  Substitution · CPC title

• B01J31/2495 Primary

  Ligands comprising a phosphine-P atom and one or more further complexing phosphorus atoms covered by groups B01J31/1845 - B01J31/1885, e.g. phosphine/phosphinate or phospholyl/phosphonate ligands · CPC title

• B01J2231/4261

  Heck-type, i.e. RY + C=C, in which R is aryl · CPC title

• C07F15/0066

  without a metal-carbon linkage · CPC title

• B01J2531/824

  Palladium · CPC title