公开(公告)号：US07649117B2

公开(公告)日：2010-01-19

申请号：US12179088

申请日：2008-07-24

申请人： Tsuneo Imamoto ,  Kazuhiro Yoshida ,  Miwako Nishimura ,  Aya Koide

发明人： Tsuneo Imamoto ,  Kazuhiro Yoshida ,  Miwako Nishimura ,  Aya Koide

IPC分类号： C07C45/65

CPC分类号： C07C45/64 ,  C07B53/00 ,  C07B2200/07 ,  C07C67/31 ,  C07C231/12 ,  C07C231/16 ,  C07C69/675 ,  C07C69/732 ,  C07C69/734 ,  C07C235/06

摘要： Disclosed is a process of preparing an optically active β-hydroxycarboxylic acid derivative comprising asymmetrically hydrogenating a β-keto compound in the presence of a catalyst comprising a transition metal complex compound having a 2,3-bis(dialkylphosphino)pyrazine derivative as a ligand. The pyrazine derivative is preferably a quinoxaline derivative, and the transition metal is preferably ruthenium. Preferred examples of the quinoxaline derivative are (S,S)-2,3-bis(tert-butylmethylphosphino)quinoxaline, (R,R)-bis(tert-butylmethylphosphino)quinoxaline, (S,S)-bis(tert-adamantylmethylphosphino)quinoxaline, and (R,R)-bis(adamantylmethylphosphino)quinoxaline.

摘要翻译： 公开了一种制备光学活性β-羟基羧酸衍生物的方法，包括在包含具有2,3-双（二烷基膦基）吡嗪衍生物作为配体的过渡金属络合物的催化剂存在下不对称氢化β-酮化合物的方法。 吡嗪衍生物优选为喹喔啉衍生物，过渡金属优选为钌。 喹喔啉衍生物的优选实例是（S，S）-2,3-双（叔丁基甲基膦基）喹喔啉，（R，R） - 双（叔丁基甲基膦基）喹喔啉，（S，S） - 双（叔 - 金刚烷基甲基膦基 ）喹喔啉和（R，R） - 双（金刚烷基甲基膦基）喹喔啉。

公开(公告)号：US08076480B2

公开(公告)日：2011-12-13

申请号：US12179069

申请日：2008-07-24

申请人： Tsuneo Imamoto ,  Kazuhiro Yoshida ,  Miwako Nishimura ,  Aya Koide

发明人： Tsuneo Imamoto ,  Kazuhiro Yoshida ,  Miwako Nishimura ,  Aya Koide

IPC分类号： C07D241/36

CPC分类号： C07C231/12 ,  C07B53/00 ,  C07B2200/07 ,  C07C67/343 ,  C07C209/16 ,  C07C2601/14 ,  C07C69/618 ,  C07C211/08 ,  C07C211/35 ,  C07C233/51

摘要： Disclosed is a process of preparing an optically active allyl compound, e.g., as represented by formula (III): comprising asymmetrically coupling an allyl compound with an organic nucleophilic compound in the presence of a catalyst. The catalyst is preferably a transition metal complex compound having a phosphine ligand. The phosphine ligand is preferably a 2,3-bis(dialkylphosphino)pyrazine derivative. The pyrazine derivative is preferably a quinoxaline derivative. The transition metal is preferably palladium.

摘要翻译： 公开了制备光学活性烯丙基化合物的方法，例如由式（III）表示的方法：包括在催化剂存在下使烯丙基化合物与有机亲核化合物不对称偶合。 催化剂优选为具有膦配体的过渡金属络合物。 膦配体优选为2,3-双（二烷基膦基）吡嗪衍生物。 吡嗪衍生物优选为喹喔啉衍生物。 过渡金属优选为钯。

公开(公告)号：US07534920B2

公开(公告)日：2009-05-19

申请号：US12073415

申请日：2008-03-05

申请人： Tsuneo Imamoto ,  Kazuhiro Yoshida ,  Youichi Saitoh ,  Aya Koide

发明人： Tsuneo Imamoto ,  Kazuhiro Yoshida ,  Youichi Saitoh ,  Aya Koide

IPC分类号： C07F9/02

CPC分类号： C07F9/5027 ,  C07B53/00 ,  C07F9/5013

摘要： An optically-active bis(alkynylphosphino)ethane-borane derivative represented by formula (1): wherein R1 and R2, which may be the same or different, each represent an alkyl group, a phenyl group, an alkylsilyl group or a hydrogen atom; R3 represents a branched alkyl group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group; and the asterisk * indicates an optically-active site. The derivative (1) is prepared by bromination of, e.g., an (S)-t-butylmethylphosphine-borane, reaction with an alkynyl lithium, deprotonation, followed by oxidative coupling. Deprotection of the derivative (1) by deboranation gives an optically-active bis(alkynylphosphino)ethane derivative useful as a ligand providing an asymmetric catalyst for catalytic asymmetric synthesis. The asymmetric catalyst having the ligand exhibits high selectivity and catalyst activity.

摘要翻译： 由式（1）表示的光学活性双（炔基膦基）乙烷 - 硼烷衍生物：其中R1和R2可以相同或不同，各自表示烷基，苯基，烷基甲硅烷基或氢原子; R3表示支链烷基，脂环族烃基或芳香族烃基; 星号*表示光学活性位点。 衍生物（1）通过例如（S） - 叔丁基甲基膦 - 硼烷的溴化，与炔基锂的反应，去质子化，然后进行氧化偶联来制备。 衍生物（1）通过脱硼脱保护得到用作催化不对称合成的不对称催化剂的配体的光学活性双（炔基膦基）乙烷衍生物。 具有配体的不对称催化剂表现出高选择性和催化剂活性。

公开(公告)号：US20080221362A1

公开(公告)日：2008-09-11

申请号：US12073415

申请日：2008-03-05

申请人： Tsuneo Imamoto ,  Kazuhiro Yoshida ,  Youichi Saitoh ,  Aya Koide

发明人： Tsuneo Imamoto ,  Kazuhiro Yoshida ,  Youichi Saitoh ,  Aya Koide

IPC分类号： C07F9/54

CPC分类号： C07F9/5027 ,  C07B53/00 ,  C07F9/5013

摘要： An optically-active bis(alkynylphosphino)ethane-borane derivative represented by formula (1): wherein R1 and R2, which may be the same or different, each represent an alkyl group, a phenyl group, an alkylsilyl group or a hydrogen atom; R3 represents a branched alkyl group, an alicyclic hydrocarbon group or an aromatic hydrocarbon group; and the asterisk * indicates an optically-active site. The derivative (1) is prepared by bromination of, e.g., an (S)-t-butylmethylphosphine-borane, reaction with an alkynyl lithium, deprotonation, followed by oxidative coupling. Deprotection of the derivative (1) by deboranation gives an optically-active bis(alkynylphosphino)ethane derivative useful as a ligand providing an asymmetric catalyst for catalytic asymmetric synthesis. The asymmetric catalyst having the ligand exhibits high selectivity and catalyst activity.

摘要翻译： 由式（1）表示的光学活性双（炔基膦基）乙烷 - 硼烷衍生物：其中R 1和R 2可以相同或不同，表示 烷基，苯基，烷基甲硅烷基或氢原子; R 3表示支链烷基，脂环族烃基或芳香族烃基; 星号*表示光学活性位点。 衍生物（1）通过例如（S） - 叔丁基甲基膦 - 硼烷的溴化，与炔基锂的反应，去质子化，然后进行氧化偶联来制备。 衍生物（1）通过脱硼脱保护得到用作催化不对称合成的不对称催化剂的配体的光学活性双（炔基膦基）乙烷衍生物。 具有配体的不对称催化剂表现出高选择性和催化剂活性。

公开(公告)号：US20070021610A1

公开(公告)日：2007-01-25

申请号：US11359369

申请日：2006-02-23

申请人： Tsuneo Imamoto ,  Kazuhiro Yoshida ,  Keitaro Sugita

发明人： Tsuneo Imamoto ,  Kazuhiro Yoshida ,  Keitaro Sugita

IPC分类号： C07F15/00 ,  C07F9/6509

CPC分类号： C07F15/008 ,  C07F9/650952

摘要： An optically active 2,3-bis(dialkylphosphino)pyrazine derivative represented by formula (1) is disclosed. The pyrazine derivative is preferably a quinoxaline derivative represented by formula (2). In formula (1) and (2), R1 is preferably a t-butyl or adamantyl group, and R2 is preferably a methyl group. wherein R1 is a substituted or unsubstituted, straight chain or branched alkyl group having 2 to 10 carbon atoms; R2 is a substituted or unsubstituted, straight chain or branched alkyl group having fewer carbon atoms than R1; and R3 and R4, which may be the same or different, are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or R3 and R4 are taken together to form a saturated or unsaturated ring. wherein R1 and R2 are as defined above; and R5 is a monovalent substituent.

摘要翻译： 公开了由式（1）表示的光学活性2,3-双（二烷基膦基）吡嗪衍生物。 吡嗪衍生物优选为式（2）表示的喹喔啉衍生物。 式（1）和（2）中，R 1优选为叔丁基或金刚烷基，R 2优选为甲基。 其中R 1是具有2至10个碳原子的取代或未取代的直链或支链烷基; R 2是具有比R 1更少的碳原子的取代或未取代的直链或支链烷基; R 3和R 4可以相同或不同，分别为氢原子或具有1-6个碳原子的烷基，或R“ 3和R 4一起形成饱和或不饱和的环。 其中R 1和R 2如上定义; R 5是一价取代基。

公开(公告)号：US07608709B2

公开(公告)日：2009-10-27

申请号：US11359369

申请日：2006-02-23

申请人： Tsuneo Imamoto ,  Kazuhiro Yoshida ,  Keitaro Sugita

发明人： Tsuneo Imamoto ,  Kazuhiro Yoshida ,  Keitaro Sugita

IPC分类号： C07F9/535

CPC分类号： C07F15/008 ,  C07F9/650952

摘要： An optically active 2,3-bis(dialkylphosphino)pyrazine derivative represented by formula (1) is disclosed. The pyrazine derivative is preferably a quinoxaline derivative represented by formula (2). In formula (1) and (2), R1 is preferably a t-butyl or adamantyl group, and R2 is preferably a methyl group. wherein R1 is a substitutable straight chain or branched alkyl group having 2 to 10 carbon atoms; R2 is a substitutable straight chain or branched alkyl group having fewer carbon atoms than R1; and R3 and R4, which may be the same or different, are each a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, or R3 and R4 are taken together to form a saturated or unsaturated ring. wherein R1 and R2 are as defined above; and R5 is a monovalent substituent.

摘要翻译： 公开了由式（1）表示的光学活性2,3-双（二烷基膦基）吡嗪衍生物。 吡嗪衍生物优选为式（2）表示的喹喔啉衍生物。 在式（1）和（2）中，R1优选为叔丁基或金刚烷基，R2优选为甲基。 其中R1是具有2-10个碳原子的可取代的直链或支链烷基; R2是具有比R1少的碳原子的可取代的直链或支链烷基; 和可以相同或不同的R 3和R 4各自为氢原子或具有1至6个碳原子的烷基，或者R 3和R 4一起形成饱和或不饱和的环。 其中R1和R2如上所定义; R5是一价取代基。

公开(公告)号：US20060211888A1

公开(公告)日：2006-09-21

申请号：US10564985

申请日：2004-07-27

申请人： Nobuhiko Oohara ,  Tsuneo Imamoto

发明人： Nobuhiko Oohara ,  Tsuneo Imamoto

IPC分类号： C07F9/02

CPC分类号： C07F9/65683 ,  C07F9/65685 ,  C07F15/008

摘要： Primary phosphine represented by formula (1): [Chem. 1] R—PH2  (1) (wherein R represents a linear, branched, or cyclic alkyl group having 2 to 20 carbon atoms) is reacted with a compound represented by formula (2): [Chem. 2] Y—CnH2n—Y  (2) (wherein Y represents a halogen atom or a leaving group selected from —OTs, —OTf, and —OMs, and n represents a number of 3 to 6) in the presence of a base; the product is reacted with boron trihydride, oxygen, or sulfur to obtain a phosphorus heterocyclic compound represented by formula (3): (wherein R represents the same as the above, n represents a number of 1 to 4, X represents a boron trihydride group, an oxygen atom, or a sulfur atom, and === represents a single bond when X is a boron trihydride group or a double bond when X is an oxygen atom or sulfur atom); the resultant compound is dimerized to produce a phosphorus heterocyclic dimer represented by formula (4): (wherein R, n, and X represent the same as the above); and then oxygen, sulfur, or borane is removed from the resultant phosphorus heterocyclic dimer to obtain an optically active phosphorus heterocyclic dimer represented by formula (5): (wherein R and n represent the same as the above).

摘要翻译： 由式（1）表示的主要膦：[Chem。 1] <？in-line-formula description =“In-line Formulas”end =“lead”？> R-PH <2>（1）<？in-line-formula description =“In- （式中，R表示碳原子数2〜20的直链状，支链状或环状的烷基）与式（2）表示的化合物反应：[化学式3] 2] <？in-line-formula description =“In-line Formulas”end =“lead”？> YC H 2n-2（2）<？in -line-formula description =“In-line Formulas”end =“tail”？>（其中Y表示卤原子或选自-OT，-OTf和-OMs的离去基团，n表示3〜 6）在碱的存在下; 使产物与三氢化硼，氧或硫反应，得到由式（3）表示的磷杂环化合物：其中R表示与上述相同的数，n表示1至4的数，X表示三氢化硼 ，氧原子或硫原子，当X是氧化硼原子或硫原子时，X表示单键或双键; 将所得化合物二聚以产生由式（4）表示的磷杂环二聚体：（其中R，n和X表示与上述相同）; 然后从得到的磷杂环二聚体中除去氧，硫或甲硼烷，得到式（5）表示的光学活性磷杂环二聚体：（其中R和n表示与上述相同的含义）。

公开(公告)号：US20140213800A1

公开(公告)日：2014-07-31

申请号：US14126683

申请日：2012-06-21

申请人： Zhenfeng Zhang ,  Tsuneo Imamoto ,  Ken Tamura

发明人： Zhenfeng Zhang ,  Tsuneo Imamoto ,  Ken Tamura

IPC分类号： C07F9/28

CPC分类号： C07F9/28 ,  C07B53/00 ,  C07C231/18 ,  C07F9/65517 ,  C07F15/0073 ,  C07C233/47

摘要： Provided are a novel 1,2-bis(dialkylphosphino)-4,5-(methylenedioxy)benzene derivative that forms a metal complex having particularly high asymmetry induction capacity and catalytic activity on β-dehydroamino acids, a method for manufacturing the same, a metal complex having this 1,2-bis(dialkylphosphino)-4,5-(methylenedioxy)benzene derivative as a ligand, and an asymmetric hydrogenation method using this metal complex. A 1,2-bis(dialkylphosphino)-4,5-(methylenedioxy)benzene derivative represented by general formula (1). (In the formula, R1 and R2 represent an alkyl group having 1-10 carbon atoms, and R1 and R2 have different numbers of carbon atoms.)

摘要翻译： 提供了形成具有特别高的不对称诱导能力和对 - 脱氨基酸的催化活性的金属络合物的新型1,2-双（二烷基膦基）-4,5-（亚甲二氧基）苯衍生物，其制造方法， 具有该1,2-二（二烷基膦基）-4,5-（亚甲二氧基）苯衍生物作为配体的金属络合物和使用该金属络合物的不对称氢化法。 由通式（1）表示的1,2-双（二烷基膦基）-4,5-（亚甲二氧基）苯衍生物。 （式中，R 1，R 2表示碳原子数1〜10的烷基，R 1和R 2的碳原子数不同。）

公开(公告)号：US20100234626A1

公开(公告)日：2010-09-16

申请号：US12719252

申请日：2010-03-08

申请人： Ken Tamura ,  Masashi Sugiya ,  Tsuneo Imamoto

发明人： Ken Tamura ,  Masashi Sugiya ,  Tsuneo Imamoto

IPC分类号： C07F15/00 ,  C07F9/535

CPC分类号： C07F15/008 ,  B01J31/2409 ,  B01J2231/645 ,  B01J2531/822 ,  C07F9/5027

摘要： It is an object of the present invention to provide a novel phosphine compound capable of forming a metal complex useful as a catalyst for various asymmetric synthesis reactions, a production method thereof, and a metal complex comprising the aforementioned compound as a ligand.A 2,2′-bis(dialkylphosphino)biphenyl compound represented by the formula (A-1). A compound represented by the formula (1) is appropriate as a catalyst for an asymmetric synthesis reaction. The biphenyl compound represented by the formula (A-1) can be obtained by subjecting a compound represented by the formula (A-2) to a coupling reaction to obtain an intermediate represented by the formula (A-3), and then subjecting the intermediate to a deboranation reaction. In the formula (A-1), R1 and R2 each independently represent a C1-C10 alkyl group, R3 represents a monovalent substituent, and n represents an integer of 0 to 4. In the formula (1), R1 represents a C2-C10 alkyl group, R2 represents an alkyl group containing fewer carbon atoms than R1, R3 represents a monovalent substituent, and n represents an integer of 0 to 4.

摘要翻译： 本发明的目的是提供能够形成可用作各种不对称合成反应的催化剂的金属络合物，其制备方法和包含上述化合物作为配体的金属络合物的新型膦化合物。 由式（A-1）表示的2,2'-双（二烷基膦基）联苯化合物。 由式（1）表示的化合物作为不对称合成反应的催化剂是合适的。 由式（A-1）表示的联苯化合物可以通过使式（A-2）表示的化合物进行偶联反应，得到式（A-3）表示的中间体，然后使 中间体到脱硼反应。 在式（A-1）中，R 1和R 2各自独立地表示C1-C10烷基，R3表示一价取代基，n表示0〜4的整数。式（1）中，R1表示C2- C10烷基，R2表示比R1少的碳原子的烷基，R3表示一价取代基，n表示0〜4的整数。

公开(公告)号：US20060189818A1

公开(公告)日：2006-08-24

申请号：US10564984

申请日：2004-07-27

申请人： Nobuhiko Oohara ,  Tsuneo Imamoto

发明人： Nobuhiko Oohara ,  Tsuneo Imamoto

IPC分类号： C07F9/02

CPC分类号： C07F9/65683 ,  C07F9/65685 ,  C07F15/008

摘要： The present invention provides a novel optically active phosphorus-chiral diphosphetane compound useful as a ligand of a transition metal catalyst which is used for catalytic asymmetric synthesis such as asymmetric hydrogenation reaction and the like, the ligand capable of creating a stable asymmetric space when coordinating to a central metal, an intermediate of the compound, and a transition metal complex catalyst having the compound as a ligand. The optically active diphosphetane compound of the present invention has a structure represented by formula (1): (wherein R represents a linear, branched, or cyclic alkyl group having 2 to 20 carbon atoms).

摘要翻译： 本发明提供了一种用作催化不对称合成如过渡金属催化剂配位体的不对称氢化反应等的新的光学活性的磷 - 手性二磷杂环丁烷化合物，该配体能够在配位时产生稳定的不对称空间 中心金属，化合物的中间体和具有该化合物作为配体的过渡金属络合物催化剂。 本发明的光学活性二峰峰化合物具有由式（1）表示的结构：其中R表示碳原子数为2〜20的直链状，支链状或环状的烷基。