Japan Science and Technology Agency

Tohoku University

Api Corporation

Norie Momiyama

Hisashi Yamamoto

Susumu Saito

Hiromi Torii

Yuhei Yamamoto

Masahiro Terada

Tohru Konno

A novel bis-phosphate compound is provided which can be applied to a wide range of reactive substrates and reactions as an asymmetric reaction catalyst and can realize an asymmetric reaction affording a high yield and a high enantiomeric excess. The bis-phosphate compound has a tetraaryl skeleton represented by General Formula (1). In an asymmetric reaction, an amidodiene and an unsaturated aldehyde compound are reacted with each other in the presence of the optically active bis-phosphate compound to give an optically active amidoaldehyde. The invention allows a reaction such as an asymmetric Diels-Alder reaction to proceed efficiently, which has been difficult with conventional mono-phosphate compounds. Thus, the invention enables an industrially feasible method for the production of optically active amidoaldehydes, optically active &#x3b2;-amino acid derivatives, optically active diamine compounds, optically active pyrrolidine derivatives and optically active dihydropyran derivatives which are useful as products such as medicines, agricultural chemicals and chemical products as well as synthesis intermediates for such products.

Bis-phosphate compound and asymmetric reaction using the same

The present invention is directed to a process of making &#x3b1;-aminooxyketone and &#x3b1;-hydroxyketone compounds. The synthetic pathway generally involves reacting an aldehyde or ketone substrate and a nitroso substrate in the presence of a catalyst of the formula (IV): wherein X-Xrepresent independently nitrogen, carbon, oxygen or sulfur and Z represents a 4 to 10-membered ring with or without a substituent and optionally a further step to convert the &#x3b1;-aminooxyketone compound formed to the &#x3b1;-hydroxyketone compound. The present invention results in &#x3b1;-aminooxyketone and &#x3b1;-hydroxyketone compounds with high enantioselectivity and high purity. The present invention is also directed to a catalytic asymmetric O-nitroso Aldol/Michael reaction. The substrates of this reaction are generally cyclic &#x3b1;,&#x3b2;-unsaturated ketone substrate and a nitroso substrate. This methodology generally involves reacting the cyclic &#x3b1;,&#x3b2;-unsaturated ketone substrate and the nitroso substrate in the presence of a proline-based catalyst, to provide a heterocyclic product.

Process of making &#x3b1;-aminooxyketone/&#x3b1;-aminooxyaldehyde and &#x3b1;-hydroxyketone/&#x3b1;-hydroxyaldehyde compounds and a process of making reaction products from cyclic &#x3b1;, &#x3b2;-unsaturated ketone substrates and nitroso substrates

The present invention is directed to a process of making &#x3b1;-aminooxyketone and &#x3b1;-hydroxyketone compounds. The synthetic pathway generally involves reacting an aldehyde or ketone substrate and a nitroso substrate in the presence of a catalyst of the formula (IV): wherein X&#x2014;Xrepresent independently nitrogen, carbon, oxygen or sulfur and Z represents a 4 to 10-membered ring with or without a substituent and optionally a further step to convert the &#x3b1;-aminooxyketone compound formed to the &#x3b1;-hydroxyketone compound. The present invention results in &#x3b1;-aminooxyketone and &#x3b1;-hydroxyketone compounds with high enantioselectivity and high purity. The present invention is also directed to a catalytic asymmetric O-nitroso Aldol/Michael reaction. The substrates of this reaction are generally cyclic &#x3b1;,&#x3b2;-unsaturated ketone substrate and a nitroso substrate. This methodology generally involves reacting the cyclic &#x3b1;,&#x3b2;-unsaturated ketone substrate and the nitroso substrate in the presence of a proline-based catalyst, to provide a heterocyclic product.

Process of making alpha-aminooxyketone/alpha-aminooxyaldehyde and alpha-hydroxyketone/alpha-hydroxyaldehyde compounds and a process making reaction products from cyclic alpha, beta-unsaturated ketone substrates and nitroso substrates

The present invention is directed to a process of making &#x3b1;-aminooxyketone and &#x3b1;-hydroxyketone compounds. The synthetic pathway involves reacting an aldehyde or ketone substrate and a nitroso substrate in the presence of a catalyst of the formula (IV): wherein X-Xrepresent independently nitrogen, carbon, oxygen or sulfur and Z represents a 4 to 10-membered ring with or without a substituent and optionally a further step to convert the &#x3b1;-aminooxyketone compound formed to the &#x3b1;-hydroxyketone compound which results in &#x3b1;-aminooxyketone and &#x3b1;-hydroxyketone compounds with high enantioselectivity and high purity. The present invention is also directed to a catalytic asymmetric O-nitroso Aldol/Michael reaction involving a cyclic &#x3b1;,&#x3b2;-unsaturated ketone substrate and a nitroso substrate. This methodology involves reacting the cyclic &#x3b1;,&#x3b2;-unsaturated ketone substrate and the nitroso substrate in the presence of a proline-based catalyst, to provide a heterocyclic product.

Process of making &#x3b1;-aminooxyketone/&#x3b1;-aminooxyaldehyde and &#x3b1;-hydroxyketone/&#x3b1;-hydroxyaldehyde compounds and a process making reaction products from cyclic &#x3b1;,&#x3b2;-unsaturated ketone substrates and nitroso substrates

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Sendai, Japan

Norie Momiyama