Bifunctional organic catalysts

Patent metadata

Field	Value
Publication number	US-9687832-B2
Application number	US-201314438543-A
Country	US
Kind code	B2
Filing date	Oct 28, 2013
Priority date	Oct 26, 2012
Publication date	Jun 27, 2017
Grant date	Jun 27, 2017

Abstract

The present invention provides a bifunctional catalyst of the formula (1): wherein: each R 1 is independently selected from an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted aralkyl group and an optionally substituted alkaryl group; Z represents a divalent organic linking moiety optionally containing one or more stereocenters; and EWG represents an electron-withdrawing group.

(R 1 ) 3 P═N—Z—NH-EWG  (1)

First claim

The invention claimed is:

1. A catalyst having the formula (2):

wherein:
each R 1 is independently selected from the group consisting of an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted aralkyl group and an optionally substituted alkaryl group;
EWG is an electron-withdrawing group selected from the group consisting of groups having the formulae —C(═X)NHR 2 , —C(═X)R 2 , —SO 2 R 2 and —C(═X)XR 2 , wherein X is selected from the group consisting of O and S, and wherein R 2 is selected from the group consisting of an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted aralkyl group and an optionally substituted alkaryl group;
R 3 , R 4 and R 5 are independently selected from the group consisting of hydrogen, an optionally substituted (C 1 -C 10 )alkyl group, an optionally substituted (C 3 -C 10 )cycloalkyl group, an optionally substituted (C 6 -C 10 )aryl group, an optionally substituted (C 4 -C 9 )heteroaryl group, an optionally substituted (C 7 -C 14 )aralkyl group, an optionally substituted (C 13 -C 20 )di-aryl-alkyl group and an optionally substituted (C 7 -C 14 )alkaryl group, or any two of R 3 , R 4 or R 5 on adjacent carbon atoms may together form a methylene chain having the formula —(CH 2 ) m —, wherein m is an integer of from 3 to 5, and wherein at least one of R 3 , R 4 and R 5 is not hydrogen; and
n is an integer of from 0 to 3.

2. A catalyst according to claim 1 , wherein each R 1 is independently selected from the group consisting of an optionally substituted (C 1 -C 10 )alkyl group, an optionally substituted (C 3 -C 10 )cycloalkyl group, an optionally substituted (C 6 -C 10 )aryl group, an optionally substituted (C 4 -C 9 )heteroaryl group, an optionally substituted (C 7 -C 14 )aralkyl group and an optionally substituted (C 7 -C 14 )alkaryl group.

3. A catalyst according to claim 1 , wherein EWG is selected from the group consisting of —C(═O)NHR 2 and —C(═S)NHR 2 , wherein R 2 is selected from the group consisting of an optionally substituted alkyl group, an optionally substituted cycloalkyl group, an optionally substituted aryl group, an optionally substituted heteroaryl group, an optionally substituted aralkyl group and an optionally substituted alkaryl group; or EWG is selected from the group consisting of —C(═O)NHR 2 and —C(═S)NHR 2 , wherein R 2 is selected from the group consisting of an optionally substituted (C 1 -C 10 )alkyl group, an optionally substituted (C 3 -C 10 )cycloalkyl group, an optionally substituted (C 6 -C 10 )aryl group, an optionally substituted (C 4 -C 9 )heteroaryl group, an optionally substituted (C 7 -C 14 )aralkyl group and an optionally substituted (C 7 -C 14 )alkaryl group.

4. A catalyst according to claim 1 , wherein EWG has the formula:

wherein:
X′ is selected from the group consisting of S and O;
R 19 is selected from the group consisting of hydrogen and —C(═Z′)N(R 21 ) 2 , wherein Z′ is selected from the group consisting of S and O, and each R 21 is independently selected from the group consisting of hydrogen, an optionally substituted (C 1 -C 10 )alkyl group, an optionally substituted (C 3 -C 10 )cycloalkyl group, an optionally substituted (C 6 -C 10 )aryl group, an optionally substituted (C 4 -C 9 )heteroaryl group, an optionally substituted (C 7 -C 14 )aralkyl group and an optionally substituted (C 7 -C 14 )alkaryl group; and
each R 20 is independently selected from the group consisting of hydrogen, an optionally substituted (C 1 -C 10 )alkyl group, an optionally substituted (C 3 -C 10 )cycloalkyl group, an optionally substituted (C 6 -C 10 )aryl group, an optionally substituted (C 4 -C 9 )heteroaryl group, an optionally substituted (C 7 -C 14 )aralkyl group and an optionally substituted (C 7 -C 14 )alkaryl group; or

EWG is:

5. A catalyst according to claim 1 , having the formula (3):

or having the formula (4);

wherein X is S or O.

6. A catalyst according to claim 5 , wherein at least one of R 3 and R 5 is selected from the group consisting of methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl, phenyl, 4-methylphenyl, 4-methoxyphenyl, 2,5-dimethyl phenyl, benzyl, 4-methoxybenzyl, diphenylmethyl, iso-propyloxymethyl and tert-butyloxymethyl, or in the case where n is 0, R 3 and R 5 may together form a methylene chain having the formula —(CH 2 ) m —, wherein m is 3 or 4.

7. A catalyst according to claim 1 , wherein n is an integer from 0 to 2.

8. A catalyst according to claim 1 , having the formula (5) or (6):

with the proviso that R 3 is not hydrogen;
or having the formula (7) or (8):

with the proviso that R 5 is not hydrogen; or having the formula (9) or (10):

with the proviso that R 3 is not hydrogen;
or having the formula (11) or (12):

with the proviso that R 5 is not hydrogen;
or having the formula (13) or (14):

with the proviso that R 3 is not hydrogen;
or having formula (15) or (16):

with the proviso that R 5 is not hydrogen;
or having the formula (17), (18), (19) or (20):

with the provisos that R 3 is not hydrogen and R 5 is not hydrogen, or having the formula (21) or (22):

with the proviso that R 3 is not hydrogen;
or having the formula (23) or (24):

with the proviso that R 5 is not hydrogen;
or having the formula (25), (26), (27) or (28):

with the provisos that R 3 is not hydrogen and R 5 is not hydrogen; or having the formula (23) or (24) wherein X is S, R 1 is phenyl or 4-methoxyphenyl, R 2 is selected from the group consisting of 4-(trifluoromethylphenyl), 3,5-bis-(trifluoromethyl)phenyl and 4-nitrophenyl, and R 5 is selected from the group consisting of iso-propyl, tert-butyl, phenyl, benzyl and diphenylmethyl.

9. A catalyst according to claim 7 , wherein n is 0 or 1.

10. A catalyst according to clai

Assignees

• Isis Innovation
• Univ Oxford Innovation Ltd

Inventors

• Dixon Darren J
• Farley Alistair J
• Núñez Marta G

Classifications

• B01J31/0241 Primary

  Imines or enamines · CPC title

• C07F9/58

  Pyridine rings · CPC title

• B01J31/0271 Primary

  also containing elements or functional groups covered by B01J31/0201 - B01J31/0231 · CPC title

• B01J31/0218

  Sulfides · CPC title

• B01J31/0249

  Ureas (R2N-C(=O)-NR2) · CPC title