公开(公告)号：US07589196B2

公开(公告)日：2009-09-15

申请号：US10552066

申请日：2004-04-05

申请人： Benoît Pugin ,  Pierre Martin ,  Markus Müller ,  Frédéric Maurice Naud ,  Felix Spindler ,  Marc Thommen ,  Gianpietro Melone ,  Martin Kesselgruber

发明人： Benoît Pugin ,  Pierre Martin ,  Markus Müller ,  Frédéric Maurice Naud ,  Felix Spindler ,  Marc Thommen ,  Gianpietro Melone ,  Martin Kesselgruber

IPC分类号： C07D265/36

CPC分类号： C07B53/00 ,  B01J31/1865 ,  B01J31/1875 ,  B01J31/2409 ,  B01J2231/323 ,  B01J2231/44 ,  B01J2231/643 ,  B01J2531/80 ,  B01J2531/821 ,  B01J2531/822 ,  B01J2531/827 ,  C07D265/36 ,  C07F9/5027 ,  C07F9/65324 ,  C07F9/65335 ,  C07F15/0033 ,  C07F15/004 ,  C07F15/0073 ,  C07F15/008

摘要： 1,1′-Biphenyl-2,2′-diphosphines having at least one amine substituent in the para position relative to the phosphine group and having the formulae are ligands for metal complexes which serve as catalysts for asymmetric addition reactions of prochiral organic compounds and whose catalytic properties can be tailored specifically to particular substrates by substitution of the amine group.

摘要翻译： 在相对于膦基的对位具有至少一个胺取代基的1,1'-联苯-2,2'-二膦具有下式：金属络合物的配体，其用作前手性有机化合物的不对称加成反应的催化剂， 其催化性能可以通过取代胺基而特异性地调整到特定的底物。

公开(公告)号：US07375241B2

公开(公告)日：2008-05-20

申请号：US10582406

申请日：2004-12-10

申请人： Matthias Lotz ,  Martin Kesselgruber ,  Marc Thommen ,  Benoît Pugin

发明人： Matthias Lotz ,  Martin Kesselgruber ,  Marc Thommen ,  Benoît Pugin

IPC分类号： C07F5/02 ,  C07F15/00 ,  C07C229/00 ,  C07C69/34

CPC分类号： C07C233/51 ,  C07B2200/07 ,  C07C67/303 ,  C07C233/48 ,  C07C2601/14 ,  C07F17/02 ,  C07C69/34

摘要： The invention relates to compounds of formula (I) provided in the form of racemic compounds, mixtures of diastereomers or essentially pure diastereomers, wherein R1 represents a hydrogen atom or C1-C4-alkyl, and at least one secondary phosphine depicts an unsubstituted or substituted cyclic phosphine group, or phosphonium salts thereof having one or two monovalent anions or a divalent anion. The compounds of formula (I) can be obtained by means of a novel method and are valuable ligands for catalytically active metal complexes in asymmetrical synthesis

摘要翻译： 本发明涉及以消旋化合物的形式提供的式（I）化合物，非对映异构体或基本上纯的非对映异构体的混合物，其中R 1表示氢原子或C 1〜 -C 4 - 亚烷基，至少一个仲膦表示未取代或取代的环膦基，或其具有一个或两个单价阴离子或二价阴离子的鏻盐。 式（I）化合物可以通过新的方法获得，并且是不对称合成中催化活性金属络合物的有价值的配体

公开(公告)号：US07435840B2

公开(公告)日：2008-10-14

申请号：US10582404

申请日：2004-12-10

申请人： Andreas Pfaltz ,  Matthias Lotz ,  Marc Schönleber ,  Benoît Pugin ,  Martin Kesselgruber ,  Marc Thommen

发明人： Andreas Pfaltz ,  Matthias Lotz ,  Marc Schönleber ,  Benoît Pugin ,  Martin Kesselgruber ,  Marc Thommen

IPC分类号： C07F15/00 ,  B01J31/00

CPC分类号： C07F9/65848 ,  C07F17/02

摘要： The invention relates to compounds having a structural element of formula (I) in an aromatic hydrocarbon ring, wherein: M represents —Li, —MgX3, (C1-C18-Alkyl)3Sn—, —ZnX3 or —B(O—C1-C4-Alkyl)2; X1 and X2, independent of one another, represent O or N, and C-bound hydrocarbon radicals or heterohydrocarbon radicals are bound to the free bonds of the O and N atoms; group —C═C—, together with C atoms, forms a hydrocarbon aromatic compound and represents X3 Cl, Br or I. The inventive compounds are easily obtained by directly substituting the hydrogen in the ortho position to the P atom with metalation reagents. The metal atoms can then be substituted by a reactive electrophilic compound. The group —P(X1—)(X2—) - - - -(BH3)0,1 can then be converted into a secondary phosphine group. The inventive method enables the production of monophosphines and diphosphines even on a large scale, which are valuable ligands for metal complexes serving as catalysts for, e.g. enantioselective hydrogenations.

摘要翻译： 本发明涉及在芳族烃环中具有式（I）结构元件的化合物，其中：M表示-Li，-MgX 3，（C 1 -C 3） 烷基）3-Sn-，-ZnX 3或-B（OC 1 -C 3） 4 - 烷基）2 然后可以转化成次膦基。 本发明的方法甚至可以大量生产单膦和二膦，这是用作金属络合物的有价值的配体，用作催化剂。 对映选择性氢化。

公开(公告)号：US20090270622A1

公开(公告)日：2009-10-29

申请号：US11887448

申请日：2006-04-19

申请人： Martin Kesselgruber ,  Marc Thommen ,  Mathias Lotz

发明人： Martin Kesselgruber ,  Marc Thommen ,  Mathias Lotz

IPC分类号： C07F15/02 ,  C07D207/00 ,  C07D333/50 ,  C07C227/00 ,  C07C67/00

CPC分类号： B41K1/28 ,  B41K1/32 ,  C07F17/02

摘要： Compounds of the formula I or I′, where the radicals R1 are each, independently of one another, a hydrogen atom or C1-C4-alkyl and R′1, is C1-C4-alkyl; X1 and X2 are each, independently of one another, a sec-phosphino group; R2 is hydrogen, R01R02R03Si— is halogen-, hydroxyl-, C1-C8-alkoxy- or R04R05N-substituted C1-C18-acyl or is R06—X01—C(O)—; R01, R02 and R03 are each, independently of one another, C1-C12-alkyl, unsubstituted or C1-C4-alkyl- or C1-C4-alkoxy-substituted C6-C10-aryl or C7-C12-aralkyl; R04 and R05 are each, independently of one another, hydrogen, C1-C12-alkyl, C3-C8-cycloalkyl, C6-C10-aryl or C7-C12-aralkyl, or R04 and R05 together are trimethylene, tetramethylene, pentamethylene or 3-oxapentylene; R06 is C1-C18-alkyl, unsubstituted or C1-C4-alkyl- or C1-C4-alkoxy-substituted C3-C8-cycloalkyl, C6-C10-aryl or C7-C12-aralkyl; X01 is —O— or —NH—; T is C-bonded C3-C20-heteroarylene; v is 0 or an integer from 1 to 4; X1 in the heteroring of the heteroarylene is bound in the ortho position relative to the T—C* bond; and * indicates a mixture of racemic or enantiomerically pure diastereomers or pure racemic or enantiomerically pure diastereomers. The compounds are excellent chiral ligands for metal complexes as enantioselective catalysts for the hydrogenation of prochiral organic compounds.

摘要翻译： 式I或I'的化合物，其中基团R 1各自彼此独立地为氢原子或C 1 -C 4 - 烷基且R'1为C 1 -C 4 - 烷基; X1和X2各自独立地为仲膦基; R2是氢，R01R02R03Si-是卤素，羟基，C1-C8-烷氧基 - 或R04R05N-取代的C1-C18-酰基，或是R06-X01-C（O） - ; R01，R02和R03各自独立地为C1-C12-烷基，未取代的或C1-C4-烷基 - 或C1-C4-烷氧基取代的C6-C10-芳基或C7-C12-芳烷基; R 04和R 05彼此独立地为氢，C 1 -C 12 - 烷基，C 3 -C 8 - 环烷基，C 6 -C 10 - 芳基或C 7 -C 12 - 芳烷基，或R 04和R 05一起是三亚甲基，四亚甲基，五亚甲基或3 - 氧亚辛 R06是C1-C18-烷基，未取代的或C1-C4-烷基 - 或C1-C4-烷氧基取代的C3-C8-环烷基，C6-C10-芳基或C7-C12-芳烷基; X01为-O-或-NH-; T是C-C 3 -C 20亚杂芳基; v为0或1至4的整数; 杂亚芳基的杂环中的X 1相对于T-C *键在邻位结合; 和*表示外消旋或对映体纯的非对映异构体或纯外消旋或对映体纯的非对映异构体的混合物。 该化合物是金属络合物的优异手性配体，作为用于前手性有机化合物氢化的对映选择性催化剂。

公开(公告)号：US07491671B2

公开(公告)日：2009-02-17

申请号：US10556084

申请日：2004-05-07

申请人： Martin Kesselgruber ,  Marc Thommen

发明人： Martin Kesselgruber ,  Marc Thommen

IPC分类号： B01J31/00

CPC分类号： B01J31/1845 ,  B01J2231/643 ,  B01J2231/645 ,  B01J2531/023 ,  B01J2531/821 ,  B01J2531/822 ,  B01J2531/827 ,  C07B53/00 ,  C07B2200/07 ,  C07C67/303 ,  C07F9/65683 ,  C07F9/65688 ,  C07C69/34

摘要： Process for preparing a catalyst solution by reacting metal complexes and diphosphines in the presence of an inert organic solvent, which is characterized in that a) an uncharged or cationic metal complex having a TM8 metal as central atom, and b) a salt of a chiral ditertiary diphosphine which has one or two phospholane groups which are bound to a carbon chain having from 2 to 4 carbon atoms and contain anions selected from the group consisting of RCCOO−, RCSO3−, BF4−, PF6−, AsF6−, SbF6−, B(C6F5)4− and B(3,5-bistrifluoromethylphenyl)4−, are reacted with one another, where the ratio of the components a) and b) is from 1:1 to 1:2 and RC is C1-C6-haloalkyl, C5-C10-halocycloalkyl or C6-C10-haloaryl.

摘要翻译： 一种在惰性有机溶剂存在下使金属配合物和二膦反应制备催化剂溶液的方法，其特征在于：a）具有TM8金属作为中心原子的不带电荷或阳离子金属络合物，和b）手性 具有一个或两个磷酸基团的二重二膦，其与具有2至4个碳原子的碳链结合并含有选自RCCOO-，RCSO3-，BF4-，PF6-，AsF6-，SbF6-， B（C 6 F 5）4-和B（3,5-双三氟甲基苯基）4-彼此反应，其中组分a）和b）的比例为1:1至1:2，RC为C1-C6 C 5 -C 10 - 卤代环烷基或C 6 -C 10 - 卤代芳基。

公开(公告)号：US07244860B2

公开(公告)日：2007-07-17

申请号：US10556085

申请日：2004-05-07

申请人： Felix Spindler ,  Matthias Lotz ,  Marc Thommen

发明人： Felix Spindler ,  Matthias Lotz ,  Marc Thommen

IPC分类号： C07C69/63

CPC分类号： B01J31/2409 ,  B01J31/2295 ,  B01J2231/645 ,  B01J2531/0286 ,  B01J2531/821 ,  B01J2531/822 ,  B01J2531/827 ,  C07B53/00 ,  C07F17/02

摘要： Compounds of the formula (I), in which R1 is C1-C4alkyl, C6-C10aryi or C7-C11, aralkyl, R2 is an open-chain or cyclic secondary amino group, and R is a radical of the formula in which R3 is C1-C4alkyl or C1-C4alkoxy, and R4 is H, C1-C4alkyl or C1-C4alkoxy, are ligands for metal complexes as homogeneous hydrogenation catalysts for prochiral organic compounds containing double bonds, by means of which a very high activity and productivity and also enantioselectivity can be achieved

摘要翻译： 式（I）化合物，其中R 1是C 1 -C 4烷基，C 6 - -C 10芳基或C 7 -C 11芳烷基，R 2是开链或环状的 仲氨基，R是下式的基团，其中R 3是C 1 -C 4烷基或C 1 -C 4烷基， C 1 -C 4烷氧基，R 4是H，C 1 -C 4烷基或C 1 -C 4烷基或C 作为具有双键的前置手性有机化合物的均匀氢化催化剂的金属配合物的配体，通过其具有非常高的活性和生产率以及对映选择性 可以实现

公开(公告)号：US20060241315A1

公开(公告)日：2006-10-26

申请号：US10556085

申请日：2004-05-07

申请人： Felix Spindler ,  Matthias Lotz ,  Marc Thommen

发明人： Felix Spindler ,  Matthias Lotz ,  Marc Thommen

IPC分类号： C07F17/02

CPC分类号： B01J31/2409 ,  B01J31/2295 ,  B01J2231/645 ,  B01J2531/0286 ,  B01J2531/821 ,  B01J2531/822 ,  B01J2531/827 ,  C07B53/00 ,  C07F17/02

摘要： Compounds of the formula (1), in which R1 is C1-C4alkyl, C6-C10aryi or C7-C11,aralkyl, R2 is an open-chain or cyclic secondary amino group, and R is a radical of the formula in which R3 is C1-C4alkyl or C1-C4alkoxy, and R4 is H, Cl-C4alkyl or C1-C4alkyloxy, are ligands for metal complexes as homogeneous hydrogenation catalysts for prochiral organic compounds containing double bonds, by means of which a very high activity and productivity and also enantioselectivity can be achieved.

摘要翻译： 式（1）的化合物，其中R 1是C 1 -C 4烷基，C 6 - -C 10芳基或C 7 -C 11芳烷基，R 2是开链或环状的 仲氨基，R是下式的基团，其中R 3是C 1 -C 4烷基或C 1 -C 4烷基， C 1 -C 4烷基，R 4是H，C 1 -C 4烷基或C 1 -C 4烷基， -C 4烷基氧基是金属络合物作为含双键的前置手性有机化合物的均匀氢化催化剂的配位体，通过这些配体可以获得非常高的活性和生产率以及对映选择性。

公开(公告)号：US07863447B2

公开(公告)日：2011-01-04

申请号：US11887448

申请日：2006-04-19

申请人： Martin Kesselgruber ,  Marc Thommen ,  Matthias Lotz

发明人： Martin Kesselgruber ,  Marc Thommen ,  Matthias Lotz

IPC分类号： C07F15/02 ,  C07F9/02

CPC分类号： B41K1/28 ,  B41K1/32 ,  C07F17/02

摘要： A compound of the formula I or I′, where the radicals R1 are each, independently of one another, a hydrogen atom or C1-C4-alkyl and R′1 is C1-C4-alkyl; X1 and X2 are each, independently of one another, a sec-phosphino group; R2 is (1) hydrogen, (2) R01R02R03Si—, (3) C1-C18-acyl substituted with halogen, hydroxyl, C1-C8-alkoxy or R04R05N—, or (4) R06—X01—C(O)—; R01, R02 and R03 are each, independently of one another, C1-C12-alkyl, unsubstituted or C1-C4-alkyl- or C1-C4-alkoxy-substituted C6-C10-aryl or C7-C12-aralkyl; R04 and R05 are each, independently of one another, hydrogen, C1-C12-alkyl, C3-C8-cycloalkyl, C6-C10-aryl or C7-C12-aralkyl, or R04 and R05 together are trimethylene, tetramethylene, pentamethylene or 3-oxapentylene; R06 is C1-C18-alkyl, unsubstituted or C1-C4-alkyl- or C1-C4-alkoxy-substituted C3-C8-cycloalkyl, C6-C10-aryl or C7-C12-aralkyl; X01 is —O— or —NH—; T is C-bonded C3-C20-heteroarylene; v is 0 or an integer from 1 to 4; X1 in the heteroring of the heteroarylene is bound in the ortho position relative to the T—C* bond; and * indicates a mixture of racemic or enantiomerically pure diastereomers or pure racemic or enantiomerically pure diastereomers.

摘要翻译： 式I或I'的化合物，其中基团R 1各自彼此独立地为氢原子或C 1 -C 4 - 烷基，R 11为C 1 -C 4 - 烷基; X1和X2各自独立地为仲膦基; R2是（1）氢，（2）R01R02R03Si-，（3）被卤素，羟基，C1-C8-烷氧基或R04R05N-或（4）R06-X01-C（O） - 取代的C1-C18-酰基。 R01，R02和R03各自独立地为C1-C12-烷基，未取代的或C1-C4-烷基 - 或C1-C4-烷氧基取代的C6-C10-芳基或C7-C12-芳烷基; R 04和R 05彼此独立地为氢，C 1 -C 12 - 烷基，C 3 -C 8 - 环烷基，C 6 -C 10 - 芳基或C 7 -C 12 - 芳烷基，或R 04和R 05一起是三亚甲基，四亚甲基，五亚甲基或3 - 氧亚辛 R06是C1-C18-烷基，未取代的或C1-C4-烷基 - 或C1-C4-烷氧基取代的C3-C8-环烷基，C6-C10-芳基或C7-C12-芳烷基; X01为-O-或-NH-; T是C-C 3 -C 20亚杂芳基; v为0或1至4的整数; 杂亚芳基的杂环中的X 1相对于T-C *键在邻位结合; 和*表示外消旋或对映体纯的非对映异构体或纯外消旋或对映体纯的非对映异构体的混合物。

公开(公告)号：US20070015925A1

公开(公告)日：2007-01-18

申请号：US10556084

申请日：2004-05-07

申请人： Martin Kesselgruber ,  Marc Thommen

发明人： Martin Kesselgruber ,  Marc Thommen

IPC分类号： C07F9/6553 ,  C07F9/547

CPC分类号： B01J31/1845 ,  B01J2231/643 ,  B01J2231/645 ,  B01J2531/023 ,  B01J2531/821 ,  B01J2531/822 ,  B01J2531/827 ,  C07B53/00 ,  C07B2200/07 ,  C07C67/303 ,  C07F9/65683 ,  C07F9/65688 ,  C07C69/34

摘要： Process for preparing a catalyst solution by reacting metal complexes and diphosphines in the presence of an inert organic solvent, which is characterized in that a) an uncharged or cationic metal complex having a TM8 metal as central atom, and b) a salt of a chiral ditertiary diphosphine which has one or two phospholane groups which are bound to a carbon chain having from 2 to 4 carbon atoms and contain anions selected from the group consisting of RCCOO−, RCSO3−, BF4−, PF6−, AsF6−, SbF6−, B(C6F5)4− and B(3,5-bistrifluoromethylphenyl)4−, are reacted with one another, where the ratio of the components a) and b) is from 1:1 to 1:2 and RC is C1-C6-haloalkyl, C5-C10-halocycloalkyl or C6-C10-haloaryl.

摘要翻译： 一种在惰性有机溶剂存在下使金属配合物和二膦反应制备催化剂溶液的方法，其特征在于：a）具有TM8金属作为中心原子的不带电荷或阳离子金属络合物，和b）手性 具有一个或两个磷酸基的二重二膦与二碳原子数为2-4的碳链结合，并含有选自下列基团的阴离子：R 1 COO - PF 3，SO 3，SO 3，SO 3，SO 3，SO 3， SbF 6，其中，AsF 6，SbF 6，S 6，S 6， B（3,5-二（三氟甲基苯基））4（C 6 H 5）5 其中组分a）和b）的比例为1:1至1:2，R is为 C 1 -C 6 - 卤代烷基，C 5 -C 10 - 卤代环烷基或C 6 - - N 10 - 芳基。

公开(公告)号：US20070149796A1

公开(公告)日：2007-06-28

申请号：US10582404

申请日：2004-12-10

申请人： Andreas Pfaltz ,  Matthias Lotz ,  Marc Schonleber ,  Benoit Pugin ,  Martin Kesselgruber ,  Marc Thommen

发明人： Andreas Pfaltz ,  Matthias Lotz ,  Marc Schonleber ,  Benoit Pugin ,  Martin Kesselgruber ,  Marc Thommen

IPC分类号： C07F17/02

CPC分类号： C07F9/65848 ,  C07F17/02

摘要： The invention relates to compounds having a structural element of formula (I) in an aromatic hydrocarbon ring, wherein: M represents —Li, —MgX3, (C1-C18-Alkyl)3Sn—, —ZnX3 or —B(O—C1C4-Alkyl)2; X1 and X2, independent of one another, represent O or N, and C-bound hydrocarbon radicals or heterohydrocarbon radicals are bound to the free bonds of the O and N atoms; group —C═C—, together with C atoms, forms a hydrocarbon aromatic compound and represents X3 Cl, Br or I. The inventive compounds are easily obtained by directly substituting the hydrogen in the ortho position to the P atom with metalation reagents. The metal atoms can then be substituted by a reactive electrophilic compound. The group —P(X1—)(X2—) - - - (BH3)0,1 can then be converted into a secondary phosphine group. The inventive method enables the production of monophosphines and diphosphines even on a large scale, which are valuable ligands for metal complexes serving as catalysts for, e.g. enantioselective hydrogenations.

摘要翻译： 本发明涉及在芳族烃环中具有式（I）结构元件的化合物，其中：M表示-Li，-MgX 3，（C 1 -C 3） 烷基）3-Sn-，-ZnX 3或-B（OC 1 -C 4） 仲烷基）2