Catalysis using phosphine oxide and sulfoxide compounds

Details Catalysis using phosphine oxide and sulfoxide compounds Catalysis using phosphine oxide and sulfoxide compounds

2001-07-06

2004-07-13

Keys, Rosalynd (Department: 1621)

Organic compounds -- part of the class 532-570 series

Organic compounds

Oxygen containing

C568S643000, C585S425000, C585S427000, C564S337000

Reexamination Certificate

active

06762330

ABSTRACT:

FIELD OF INVENTION
The invention relates to the use of phosphine oxide and sulfoxide compounds complexed with transition metals to produce biaryls and arylamines via cross-coupling reactions with aryl halides and arylboronic acids, aryl Grignard reagents, or amines.
BACKGROUND
Chelating phosphine compounds when bound to metal atoms are generally known to be useful as catalysts. One reaction which uses palladium phosphine catalysts is the coupling of aryl halides with amines for the production of arylamines, as reviewed by Hartwig,
SYNLETT
, 1997, (4), pg. 329-340. An example of this reaction is the coupling of chlorobenzene and piperidine to form N-phenylpiperidine:
Another reaction in which palladium/phosphine catalysts have been used is the Suzuki reaction, where biaryls are produced through the coupling of arylboronic acids and aryl halides, as reviewed by Suzuki, A, J.
Orgmet. Chem
., 576 (1999), pg. 147. One example of this reaction is the preparation of biphenyl from phenylboronic acid and chlorobenzene:
Both of these products are important classes of compounds widely used in the manufacture of pharmaceuticals, advanced materials, liquid polymers and ligands, and much work has been done on their preparation. However, there is an expanding need for stable, easily prepared catalysts that result in good yields and mild reaction conditions.
Preparation of new ligands has traditionally been performed one at a time after tedious synthesis and purification protocols. Combinatorial techniques have greatly accelerated the discovery of new ligands, but new synthetic schemes are needed. One valuable technique uses solid-phase supports. This solid-phase protocol allows reactions on a polymer-bound scaffold to be driven to completion by using large excesses of reagents in solution that can be easily filtered away from the polymer support. After the scaffold has been modified, an additional cleavage step then frees the small molecule from the polymer support into solution for isolation.
Phosphine oxide compounds and libraries have been prepared using polymer scaffolds in U.S. application Ser. No. 09/415,347 (U.S. Ser. No. 99/23509) which is incorporated in its entirety by reference. Lacking is a process for the convenient preparation of stable arylamines of the formula R
1
—NR
2
R
3
or biaryls of the formula R
1
-R
6
using a stable phosphine catalyst under mild conditions and producing good yields.
SUMMARY OF THE INVENTION
This invention is directed to the use of phosphine oxide compounds complexed with transition metals to produce biaryls and arylamines, arylthiol, arylphosphine oxides and derivatives thereof, via cross-coupling reactions of aryl halides with arylboronic acids, arylmagnesium halides, amines, thiols, and phosphine oxides.
More specifically, the invention is directed twoards a process to prepare biaryls of the formula R
1
-R
7
comprising contacting a Grignard reagent of the formula R
7
—MgX with an aryl compound of the formula R
1
—X in the presence of a catalytic amount of a coordination compound comprising one or more transition metals complexed to a phosphine oxide compound of the formula HP(O)R
4
R
5
, wherein X is a halogen; R
1
is an optionally substituted aryl; R
7
is selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocyclic; and R
4
and R
5
are independently selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heterocyclic, organometallic, Cl, Br, I, SQ
1
, OQ
2
, PQ
3
Q
4
, and NQ
5
Q
6
, where Q
1
, Q
2
, Q
3
, Q
4
, Q
5
, and Q
6
are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocyclic, and optionally R
4
and R
5
can together form a ring.
Further, the invention includes a method for the use of phosphine oxides as ligands for homogeneous catalysis biaryls of the formula R
1
-R
7
comprising: (1) preparing a coordination compound comprising one or more transition metals complexed to a phosphine oxide compound of the formula HP(O)R
4
R
5
, wherein X is a halogen; R
1
is an optionally substituted aryl; R
7
is selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocyclic; and R
4
and R
5
are independently selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heterocyclic, organometallic, Cl, Br, I, SQ
1
, OQ
2
, PQ
3
Q
4
, and NQ
5
Q
6
, where Q
1
, Q
2
, Q
3
, Q
4
, Q
5
, and Q
6
are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocyclic, and optionally R
4
and R
5
can together form a ring; and 2) contacting a Grignard reagent of the formula R
7
—Mgx with an aryl compound of the formula R
1
—X in the presence of a catalytic amount of the coordination compound prepared in step (1) to form biaryls of the formula R
1
-R
7
.
The invention is also directed to a process to prepare biaryls of the formula R
1
-R
7
comprising contacting a Grignard reagent of the formula R
7
—Mgx with an aryl compound of the formula R
1
—X in the presence of a catalytic amount of a coordination compound comprising one or more transition metals complexed to a phosphine sulfoxide compound of the formula HP(S)R
4
R
5
, wherein X is a halogen; R
1
is an optionally substituted aryl; R
7
is selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocyclic; and R
4
and R
5
are independently selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heterocyclic, organometallic, Cl, Br, I, SQ
1
, OQ
2
, PQ
3
Q
4
, and NQ
5
Q
6
, where Q
1
, Q
2
, Q
3
, Q
4
, Q
5
, and Q
6
are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocyclic, and optionally R
4
and R
5
can together form a ring.
The invention is further directed to a process to prepare biaryls of the formula R
1
-R
6
comprising contacting a boronic acid of the formula R
6
—B(OH)
2
with an aryl compound of the formula R
1
—X in the presence of a catalytic amount of a coordination compound selected from the group consisting of {[(t-Bu)
2
P(OH)]
2
PdCl]}
2
, [(t-Bu)
2
P(OH)PdCl
2
]
2
, and [(t-Bu)
2
P(Cl)PdCl
2
]
2
, wherein X is a halogen; R
1
is an optionally substituted aryl; R
6
is selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocyclic; and R
4
and R
5
are independently selected from the group consisting of hydrocarbyl, substituted hydrocarbyl, heterocyclic, organometallic, Cl, Br, I, SQ
1
, OQ
2
, PQ
3
Q
4
, and NQ
5
Q
6
, where Q
1
, Q
2
, Q
3
, Q
4
, Q
5
, and Q
6
are independently selected from the group consisting of hydrogen, hydrocarbyl, substituted hydrocarbyl, hydrocarbylamino, alkoxy, aryloxy, and heterocyclic, and optionally R
4
and R
5
can together form a ring.
The invention is also directed to a process to prepare biaryls of the formula R
1
-R
6
comprising contacting a boronic acid of the formula R
6
—B(OH)
2
with an aryl compound of the formula R
1
—X in the presence of a catalytic amount of a coordination compound comprising one or more transition metals complexed to a phosphine oxide compound of the formula HP(O)R
4
R
5
, wherein X is a halogen; R
1
is selected from the group consisting of 3-methoxylphenyl, 2-methoxyphenyl, 4-thiomethoxyphenyl and phenyl; R
6
is phenyl; and R
4
and R
5
are t-butyl.
The invention is also directed to a process to prepare diaryl ketones of the formula R
1
—C(═O)—R
6
comprising contacting a a boronic acid of the formula R
6
—B(OH)
2
with a carbonate salt and an aryl compound of the formula R
1
—X in the presence of a catalytic amount of a coordination compound comprising one or more transition metals complexed to a phosphine oxide compound of the formula HP(O)R
4
R
5
, wherein X is a hal

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