Binaphthol monophosphoric acid derivative and its use

Details Binaphthol monophosphoric acid derivative and its use Binaphthol monophosphoric acid derivative and its use

2000-03-22

2001-08-14

Vollano, Jean F. (Department: 1621)

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

Organic compounds

Heterocyclic carbon compounds containing a hetero ring...

C549S356000, C549S028000, C558S073000, C558S083000, C562S019000

Reexamination Certificate

active

06274745

ABSTRACT:

BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to optically active binaphthol monophosphoric acid derivatives, optically active binaphthol monophosphate derivatives and their use. The optically active binaphthol monophosphate acid derivatives of the present invention are important as in intermediates for synthesis of various catalysts for asymmetric synthesis, and the binaphthol monophosphate derivatives derived therefrom have high reactivity in various asymmetric synthetic reactions and provide reaction products having a high optical purity. Pyran compounds obtained by the method of the present invention are useful compounds as intermediates for synthesis of pharmaceutical and agricultural chemicals.
2. Discussion of Background
The binaphthol monophosphoric acid derivatives of the present invention and the binaphthol monophosphate derivatives derived therefrom, have not been conventionally known, and they are novel compounds.
As one example of reactions to which the catalyst for asymmetric synthesis of the present invention is applicable, Diels-Alder cyclization reaction will be explained below.
As the Diels-Alder cyclization reaction, many reactions of a diene with an olefin in the presence or absence of a Lewis acid catalyst such as aluminum chloride, have been known for a long time.
As an asymmetric Diels-Alder cyclization reaction, e.g. a reaction of acryl-1,3-oxazolidin-2-one with cyclopentadiene has been known (Shu Kobayashi et al, J. Org. Chem., 1994, 59, 3758).
As an asymmetric hetero Diels-Alder cyclization reaction, e.g. a reaction of a benzaldehyde with a diene has been known (Hisashi Yamamoto et al, J. Am. Chem. 1988, 110, 310).
However, with respect to the conventional asymmetric Diels-Alder cyclization reactions and asymmetric hetero Diels-Alder cyclization reactions, the reaction temperature is as low as at most −20° C. in all known reactions, whereby these reactions are not satisfactory as an industrial production method, although a reaction product having a high optical purity may be obtained in some of these reactions.
SUMMARY OF THE INVENTION
The present invention has been made to overcome the above object, and it is an object of the present invention to provide a novel binaphthol monophosphate derivative useful as a catalyst for asymmetric synthesis which can be used under more practical reaction conditions and which provides a high optical purity, and its intermediate binaphthol monophosphoric acid derivative.
The present inventors have conducted extensive studies to develop a catalyst for asymmetric synthesis which can be used under more practical reaction conditions and which provides a high optical purity, and as a result, they have found a binaphthol monophosphoric acid derivative of the following formula (1) or (2):
wherein each of R
1
, R
2
, R
3
and R
4
which are independent of one another, is hydrogen, a C
1-20
linear or branched alkyl group, a C
2-20
linear or branched alkenyl group, a C
2-20
linear or branched alkynyl group, a phenyl group, a phenyl group having its nucleus substituted at the 1- to 4-carbon atom by a C
1-10
linear or branched alkyl group, a phenyl group having its nucleus substituted at the 1- to 4-carbon atom by a C
2-10
linear or branched alkenyl group, a phenyl group having its nucleus substituted at the 1- to 4-carbon atom by a C
2-10
linear or branched alkynyl group, a naphthyl group or a C
3-8
cycloalkyl group, provided that R
1
to R
4
are not simultaneously hydrogen; and a novel binaphthol monophosphoric acid derivative of the following formula (3) or (4) derived from a known compound:
wherein each of R
5
, R
6
, R
7
and R
8
which are independent of one another, is hydrogen, a C
1-20
linear or branched alkyl group, a C
1-20
linear or branched alkenyl group, a C
2-20
linear or branched alkynyl group, a phenyl group, a phenyl group having its nucleus substituted at the 1- to 4-carbon atom by a C
1-10
linear or branched alkyl group, a phenyl group having its nucleus substituted at the 1- to 4-carbon atom by a C
2-10
linear or branched alkenyl group, a phenyl group having its nucleus substituted at the 1- to 4-carbon atom by a C
2-10
linear or branched alkynyl group, a naphthyl group or a C
3-8
cycloalkyl group. Further, they have found a binaphthol monophosphate derivative of the following formula (5), (6), (7) or (8):
wherein each of R
1
, R
2
, R
3
and R
4
which are independent of one another, is hydrogen, a C
1-20
linear or branched alkyl group, a C
2-20
linear or branched alkenyl group, a C
2-20
linear or branched alkynyl group, a phenyl group, a phenyl group having its nucleus substituted at the 1- to 4-carbon atom by a C
1-10
linear or branched alkyl group, a a phenyl group having its nucleus substituted at the 1- to to 4-carbon atom by a C
2-10
linear or branched alkenyl group, a phenyl group having its nucleus substituted at the 1- to 4-carbon atom by a C
2-10
linear or branched alkynyl group, a naphthyl group or a C
3-8
cycloalkyl group, provided that R
1
to R
4
are not simultaneously hydrogen, and M is a metal element capable of forming a trivalent metal ion,
wherein each of R
5
, R
6
, R
7
and R
8
which are independent of one another, is hydrogen, a C
1-20
linear or branched alkyl group, a C
2-20
linear or branched alkenyl group, a C
2-20
linear or branched alkynyl group, a phenyl group, a phenyl group having its nucleus substituted at the 1- to 4-carbon atom by a C
1-10
linear or branched alkyl group, a phenyl group having its nucleus substituted at the 1- to 4-carbon atom by a C
2-10
linear or branched alkenyl group, a phenyl group having its nucleus substituted at the 1- to 4-carbon atom by a C
2-10
linear or branched alkynyl group, a naphthyl group or a C
3-8
cycloalkyl group, and M is a metal element capable of forming a trivalent metal ion; which is useful as a catalyst for asymmetric synthesis, and which is derived from the compound of the above formula (1), (2), (3) or (4). They have found that when the binaphthol monophosphate derivative is applied to an asymmetric hetero Diels-Alder cyclization reaction, the reaction can be carried out at room temperature, and the desired compound having a high optical purity can be obtained. The present invention has been accomplished on the basis of these discoveries.
Namely, the present invention provides binaphthol monophosphoric acid derivatives of the above formulae (1) to (4), binaphthol monophosphate derivatives of the above formulae (5) to (8), and their use.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The binaphthol monophosphoric acid derivatives of the above formulae (1) to (4) of the present invention, can be derived from optically active (R) or (S) binaphthol as the starting material, in several steps.
For example, the binaphthol monophosphoric acid derivative of the above formula (1) or (2) of the present invention may be obtained in accordance with e.g. methods as described in Reference Examples and Examples of the present invention, in such a manner that a commercially available optically active (R) or (S) 1,1′-binaphthyl-2,2′-diol is used as the starting material, the diol is protected, then, the starting material is converted to a halide at the 3,3′-positions and/or a halide at the 6,6′-positions, a substituent is introduced by e.g. a cross-coupling reaction, followed by a reaction with e.g. phosphorus oxychloride to obtain the binaphthol monophosphoric acid derivative of the formula (1) or (2).
Likewise, the binaphthol monophosphoric acid derivative of the above formula (3) or (4) may be obtained by using, as the starting material, commercially available optically active (R) or (S) 1,1′-binaphthyl-2,2′-diol or binaphthol derivatives obtained as an intermediate for synthesis of the binaphthol monophosphoric acid of the above formula (1) or (2), carrying out partial hydrogenation reaction in accordance with a known method (D. J. Cram, et al., J. Org. Chem., 1978, 43, 1930) to obtain a 5,6,7,8,5′,6′,7′,8′

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