公开(公告)号：US20120330038A1

公开(公告)日：2012-12-27

申请号：US13583875

申请日：2011-03-08

申请人： Masahiro Terada ,  Norie Momiyama ,  Tohru Konno

发明人： Masahiro Terada ,  Norie Momiyama ,  Tohru Konno

IPC分类号： C07F9/6574 ,  C07D307/58 ,  C07C269/06

CPC分类号： C07B53/00 ,  C07C231/18 ,  C07C269/06 ,  C07C2601/16 ,  C07D307/58 ,  C07F9/65746 ,  C07C271/24 ,  C07C271/16 ,  C07C233/76

摘要： 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 β-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.

摘要翻译： 提供了一种新型的双磷酸化合物，其可以应用于广泛的反应性底物和作为不对称反应催化剂的反应，并且可以实现提供高产率和高对映异构体过量的不对称反应。 双磷酸化合物具有由通式（1）表示的四芳基骨架。 在不对称反应中，酰胺二烯和不饱和醛化合物在光学活性双磷酸酯化合物的存在下彼此反应，得到光学活性的酰胺醛。 本发明允许诸如不对称Diels-Alder反应的反应有效地进行，这对于常规的单磷酸酯化合物是困难的。 因此，本发明使得工业上可行的方法可用于生产光学活性酰胺醛，光学活性和聚氨基酸衍生物，光学活性二胺化合物，光学活性吡咯烷衍生物和光学活性二氢吡喃衍生物，其可用作药物，农业 化学品和化学产品以及此类产品的合成中间体。

公开(公告)号：US20100099915A1

公开(公告)日：2010-04-22

申请号：US12578836

申请日：2009-10-14

申请人： Norie Momiyama ,  Hiromi Torii ,  Susumu Saito ,  Hisashi Yamamoto ,  Yuhei Yamamoto

发明人： Norie Momiyama ,  Hiromi Torii ,  Susumu Saito ,  Hisashi Yamamoto ,  Yuhei Yamamoto

IPC分类号： C07C291/06

CPC分类号： C07C291/04 ,  C07C2601/14 ,  C07D207/16 ,  C07D211/74 ,  C07D309/30 ,  C07D317/72 ,  C07D403/04

摘要： The present invention is directed to a process of making α-aminooxyketone and α-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 Xa—Xc represent 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 α-aminooxyketone compound formed to the α-hydroxyketone compound. The present invention results in α-aminooxyketone and α-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 α,β-unsaturated ketone substrate and a nitroso substrate. This methodology generally involves reacting the cyclic α,β-unsaturated ketone substrate and the nitroso substrate in the presence of a proline-based catalyst, to provide a heterocyclic product.

摘要翻译： 本发明涉及制备α-氨基氧基酮和α-羟基酮化合物的方法。 合成途径通常包括在式（Ⅳ）催化剂存在下使醛或酮底物和亚硝基底物反应：其中Xa-Xc独立地代表氮，碳，氧或硫，Z代表4至10元 具有或不具有取代基的环，以及任选的将形成的α-氨基氧基酮化合物转化为α-羟基酮化合物的步骤。 本发明产生具有高对映选择性和高纯度的α-氨基氧基酮和α-羟基酮化合物。 本发明还涉及催化不对称的O-亚硝基醛醇/迈克尔反应。 该反应的底物通常为环状α，β-不饱和酮底物和亚硝基。 该方法通常包括在脯氨酸基催化剂存在下使环状α，β-不饱和酮底物和亚硝基底物反应，得到杂环产物。

公开(公告)号：US08372985B2

公开(公告)日：2013-02-12

申请号：US13566587

申请日：2012-08-03

申请人： Norie Momiyama ,  Hiromi Torii ,  Susumu Saito ,  Hisashi Yamamoto ,  Yuhei Yamamoto

发明人： Norie Momiyama ,  Hiromi Torii ,  Susumu Saito ,  Hisashi Yamamoto ,  Yuhei Yamamoto

IPC分类号： C07D257/04

CPC分类号： C07C291/04 ,  C07C2601/14 ,  C07D207/16 ,  C07D211/74 ,  C07D309/30 ,  C07D317/72 ,  C07D403/04

摘要： The present invention is directed to a process of making α-aminooxyketone and α-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 Xa-Xc represent 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 α-aminooxyketone compound formed to the α-hydroxyketone compound. The present invention results in α-aminooxyketone and α-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 α,β-unsaturated ketone substrate and a nitroso substrate. This methodology generally involves reacting the cyclic α,β-unsaturated ketone substrate and the nitroso substrate in the presence of a proline-based catalyst, to provide a heterocyclic product.

摘要翻译： 本发明涉及制备α-氨基氧基酮和α-羟基酮化合物的方法。 合成途径通常包括在式（Ⅳ）催化剂存在下使醛或酮底物和亚硝基底物反应：其中Xa-Xc独立地代表氮，碳，氧或硫，Z代表4至10元 具有或不具有取代基的环，以及任选的将形成的α-氨基氧基酮化合物转化为α-羟基酮化合物的步骤。 本发明产生具有高对映选择性和高纯度的α-氨基氧基酮和α-羟基酮化合物。 本发明还涉及催化不对称的O-亚硝基醛醇/迈克尔反应。 该反应的底物通常为环状α，β-不饱和酮底物和亚硝基。 该方法通常包括在脯氨酸基催化剂存在下使环状α，β-不饱和酮底物和亚硝基底物反应，得到杂环产物。

公开(公告)号：US20120302792A1

公开(公告)日：2012-11-29

申请号：US13566587

申请日：2012-08-03

申请人： NORIE MOMIYAMA ,  HIROMI TORII ,  SUSUMU SAITO ,  HISASHI YAMAMOTO ,  YUHEI YAMAMOTO

发明人： NORIE MOMIYAMA ,  HIROMI TORII ,  SUSUMU SAITO ,  HISASHI YAMAMOTO ,  YUHEI YAMAMOTO

IPC分类号： C07C291/04

CPC分类号： C07C291/04 ,  C07C2601/14 ,  C07D207/16 ,  C07D211/74 ,  C07D309/30 ,  C07D317/72 ,  C07D403/04

摘要： The present invention is directed to a process of making α-aminooxyketone and α-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 Xa-Xc represent 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 α-aminooxyketone compound formed to the α-hydroxyketone compound. The present invention results in α-aminooxyketone and α-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 α,β-unsaturated ketone substrate and a nitroso substrate. This methodology generally involves reacting the cyclic α,β-unsaturated ketone substrate and the nitroso substrate in the presence of a proline-based catalyst, to provide a heterocyclic product.

摘要翻译： 本发明涉及制备α-氨基氧基酮和α-羟基酮化合物的方法。 合成途径通常包括在式（Ⅳ）催化剂存在下使醛或酮底物和亚硝基底物反应：其中Xa-Xc独立地代表氮，碳，氧或硫，Z代表4至10元 具有或不具有取代基的环，以及任选的将形成的α-氨基氧基酮化合物转化为α-羟基酮化合物的步骤。 本发明产生具有高对映选择性和高纯度的α-氨基氧基酮和α-羟基酮化合物。 本发明还涉及催化不对称的O-亚硝基醛醇/迈克尔反应。 该反应的底物通常为环状α，β-不饱和酮底物和亚硝基。 该方法通常包括在脯氨酸基催化剂存在下使环状α，β-不饱和酮底物和亚硝基底物反应，得到杂环产物。

公开(公告)号：US07872123B2

公开(公告)日：2011-01-18

申请号：US11506590

申请日：2006-08-18

申请人： Norie Momiyama ,  Hiromi Torii ,  Susumu Saito ,  Hisashi Yamamoto ,  Yuhei Yamamoto

发明人： Norie Momiyama ,  Hiromi Torii ,  Susumu Saito ,  Hisashi Yamamoto ,  Yuhei Yamamoto

IPC分类号： C07D265/02

CPC分类号： C07C291/04 ,  C07C2601/14 ,  C07D207/16 ,  C07D211/74 ,  C07D309/30 ,  C07D317/72 ,  C07D403/04

摘要： The present invention is directed to a process of making α-aminooxyketone and α-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 Xa-Xc represent 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 α-aminooxyketone compound formed to the α-hydroxyketone compound which results in α-aminooxyketone and α-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 α,β-unsaturated ketone substrate and a nitroso substrate. This methodology involves reacting the cyclic α,β-unsaturated ketone substrate and the nitroso substrate in the presence of a proline-based catalyst, to provide a heterocyclic product.

摘要翻译： 本发明涉及制备α-氨基氧基酮和α-羟基酮化合物的方法。 合成途径包括在式（Ⅳ）催化剂存在下使醛或酮底物和亚硝基底物反应：其中Xa-Xc独立地表示氮，碳，氧或硫，Z代表4至10元环 具有或不具有取代基，以及任选的另一步骤是将形成的α-氨基氧基酮化合物转化成α-羟基酮化合物，得到具有高对映选择性和高纯度的α-氨基氧基酮和α-羟基酮化合物。 本发明还涉及涉及环状α，β-不饱和酮底物和亚硝基底物的催化不对称O-亚硝基醇/迈克尔反应。 该方法包括在脯氨酸催化剂存在下使环状α，β-不饱和酮底物和亚硝基质反应，得到杂环产物。

公开(公告)号：US08420847B2

公开(公告)日：2013-04-16

申请号：US13583875

申请日：2011-03-08

申请人： Masahiro Terada ,  Norie Momiyama ,  Tohru Konno

发明人： Masahiro Terada ,  Norie Momiyama ,  Tohru Konno

IPC分类号： C07F9/6574

CPC分类号： C07B53/00 ,  C07C231/18 ,  C07C269/06 ,  C07C2601/16 ,  C07D307/58 ,  C07F9/65746 ,  C07C271/24 ,  C07C271/16 ,  C07C233/76

摘要： 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 β-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.

摘要翻译： 提供了一种新型的双磷酸化合物，其可以应用于广泛的反应性底物和作为不对称反应催化剂的反应，并且可以实现提供高产率和高对映异构体过量的不对称反应。 双磷酸化合物具有由通式（1）表示的四芳基骨架。 在不对称反应中，酰胺二烯和不饱和醛化合物在光学活性双磷酸酯化合物的存在下彼此反应，得到光学活性的酰胺醛。 本发明允许诸如不对称Diels-Alder反应的反应有效地进行，这对于常规的单磷酸酯化合物是困难的。 因此，本发明使得工业上可行的方法可用于生产光学活性酰胺醛，光学活性和聚氨基酸衍生物，光学活性二胺化合物，光学活性吡咯烷衍生物和光学活性二氢吡喃衍生物，其可用作药物，农业 化学品和化学产品以及此类产品的合成中间体。

公开(公告)号：US08252941B2

公开(公告)日：2012-08-28

申请号：US12578836

申请日：2009-10-14

申请人： Norie Momiyama ,  Hiromi Torii ,  Susumu Saito ,  Hisashi Yamamoto ,  Yuhei Yamamoto

发明人： Norie Momiyama ,  Hiromi Torii ,  Susumu Saito ,  Hisashi Yamamoto ,  Yuhei Yamamoto

IPC分类号： C07D257/04

CPC分类号： C07C291/04 ,  C07C2601/14 ,  C07D207/16 ,  C07D211/74 ,  C07D309/30 ,  C07D317/72 ,  C07D403/04

摘要： The present invention is directed to a process of making α-aminooxyketone and α-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 Xa—Xc represent 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 α-aminooxyketone compound formed to the α-hydroxyketone compound. The present invention results in α-aminooxyketone and α-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 α,β-unsaturated ketone substrate and a nitroso substrate. This methodology generally involves reacting the cyclic α,β-unsaturated ketone substrate and the nitroso substrate in the presence of a proline-based catalyst, to provide a heterocyclic product.

摘要翻译： 本发明涉及制备α-氨基氧基酮和α-羟基酮化合物的方法。 合成途径通常包括在式（Ⅳ）催化剂存在下使醛或酮底物和亚硝基底物反应：其中Xa-Xc独立地代表氮，碳，氧或硫，Z代表4至10元 具有或不具有取代基的环，以及任选的将形成的α-氨基氧基酮化合物转化为α-羟基酮化合物的步骤。 本发明产生具有高对映选择性和高纯度的α-氨基氧基酮和α-羟基酮化合物。 本发明还涉及催化不对称的O-亚硝基醛醇/迈克尔反应。 该反应的底物通常为环状α，β-不饱和酮底物和亚硝基。 该方法通常包括在脯氨酸基催化剂存在下使环状α，β-不饱和酮底物和亚硝基底物反应，得到杂环产物。

公开(公告)号：US20070037973A1

公开(公告)日：2007-02-15

申请号：US11506590

申请日：2006-10-25

申请人： Norie Momiyama ,  Hiromi Torii ,  Susumu Saito ,  Hisashi Yamamoto ,  Yuhei Yamamoto

发明人： Norie Momiyama ,  Hiromi Torii ,  Susumu Saito ,  Hisashi Yamamoto ,  Yuhei Yamamoto

IPC分类号： C07D498/04 ,  C07D261/20

CPC分类号： C07C291/04 ,  C07C2601/14 ,  C07D207/16 ,  C07D211/74 ,  C07D309/30 ,  C07D317/72 ,  C07D403/04

摘要： The present invention is directed to a process of making α-aminooxyketone and α-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 Xa—Xc represent 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 α-aminooxyketone compound formed to the α-hydroxyketone compound. The present invention results in α-aminooxyketone and α-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 α,β-unsaturated ketone substrate and a nitroso substrate. This methodology generally involves reacting the cyclic α,β-unsaturated ketone substrate and the nitroso substrate in the presence of a proline-based catalyst, to provide a heterocyclic product.

摘要翻译： 本发明涉及制备α-氨基氧基酮和α-羟基酮化合物的方法。 合成途径通常包括在式（Ⅳ）催化剂存在下，使醛或酮基质和亚硝基反应：其中X独立地表示独立地 氮，碳，氧或硫，Z表示具有或不具有取代基的4至10元环，并且任选地将形成的α-氨基氧基酮化合物转化为α-羟基酮化合物的另外步骤。 本发明产生具有高对映选择性和高纯度的α-氨基氧基酮和α-羟基酮化合物。 本发明还涉及催化不对称的O-亚硝基醛醇/迈克尔反应。 该反应的底物通常是环状α，β-不饱和酮底物和亚硝基底物。 该方法通常包括在脯氨酸基催化剂存在下使环状α，β-不饱和酮底物和亚硝基底物反应，得到杂环产物。