公开(公告)号：US20110118482A1

公开(公告)日：2011-05-19

申请号：US12734696

申请日：2008-11-14

申请人： Benoît Pugin ,  Matthias Lotz ,  Heidi Landert ,  Adrian Wyss ,  Raphael Aardoom ,  Bjõrn Gschwend ,  Andreas Pfaltz ,  Felix Spindler

发明人： Benoît Pugin ,  Matthias Lotz ,  Heidi Landert ,  Adrian Wyss ,  Raphael Aardoom ,  Bjõrn Gschwend ,  Andreas Pfaltz ,  Felix Spindler

IPC分类号： C07F9/6553 ,  C07F15/00 ,  C07F17/02 ,  C07F9/28 ,  C07F9/655 ,  C07C67/00 ,  C07C227/16

CPC分类号： C07F13/005 ,  B01J31/1875 ,  B01J31/2291 ,  B01J31/2495 ,  B01J2231/643 ,  B01J2231/645 ,  B01J2531/0238 ,  B01J2531/822 ,  B01J2531/827 ,  C07B53/00 ,  C07B2200/07 ,  C07C67/303 ,  C07C67/31 ,  C07C231/12 ,  C07C231/18 ,  C07F9/46 ,  C07F9/5004 ,  C07F9/5018 ,  C07F9/5022 ,  C07F9/5027 ,  C07F9/65515 ,  C07F9/65517 ,  C07F9/65522 ,  C07F9/655354 ,  C07F17/02 ,  C07C69/34 ,  C07C69/732 ,  C07C69/675 ,  C07C233/47

摘要： Compounds of the formula (I), in the form of mixtures comprising predominantly one diastereomer or in the form of pure diastereomers, Z1-Q-P*R0R1 (I) in which Z1 is a C-bonded, secondary phosphine group —P(R)2; in which R is in each case independently hydrocarbon radicals or heterohydrocarbon radicals, or Z1 is the —P*R0R1 group; Q is a bivalent, achiral, aromatic base skeleton, a bivalent, achiral ferrocene base skeleton, an optionally substituted bivalent cycloalkane or heterocycloalkane skeleton, or a C1-C4-alkylene skeleton, and in which base skeletons a secondary phosphine group Z1 is bonded directly to a carbon atom, or, in the case of cyclic base skeletons, directly to a carbon atom or via a C1-C4-alkylene group, and in which base skeletons a P-chiral group —P*R0R1 is bonded directly to a carbon atom, or, in the case of cyclic base skeletons, directly to a carbon atom or via a C1-C4-alkylene group to a carbon atom such that the phosphorus atoms are linked via 1 to 7 atoms of a carbon chain optionally interrupted by heteroatoms from the group of O, S, N, Fe or Si; P* is a chiral phosphorus atom; R0 is methyl or hydroxyl, and R0 is methyl when Z1 is the —P*R0R1 group; and R1 is a C-bonded optically enriched or optically pure chiral, mono- or polycyclic, nonaromatic hydrocarbon or heterohydrocarbon radical which has 3 to 12 ring atoms and 1 to 4 rings and which has a stereogenic carbon atom at least in the a position to the P—C bond; Metal complexes of these ligands are homogeneous catalysts for asymmetric addition reactions, particularly hydrogenations.

摘要翻译： 主要为一种非对映体或纯非对映体形式的混合物形式的式（I）化合物，其中Z 1为C键，仲膦基-P（R）的Z1-QP * R0R1（I） 2; 其中R各自独立地为烃基或杂烃基，或Z1为-P * R0R1基团; Q是二价，非手性，芳族碱基骨架，二价，非手性二茂铁碱骨架，任选取代的二价环烷烃或杂环烷骨架，或C1-C4-亚烷基骨架，其中，基骨架中的次膦基Z1直接键合 或在环状基团骨架的情况下直接与碳原子或C 1 -C 4 - 亚烷基直接键合，并且其中的基础骨架中，P手性基团-P * R0R1直接键合到碳上 或者在环状基骨架的情况下，直接连接到碳原子上，或者通过C1-C4-亚烷基与碳原子连接，使得磷原子通过1至7个任选被杂原子中断的碳链原子连接 由O，S，N，Fe或Si组成; P *是手性磷原子; R 0是甲基或羟基，当Z 1是-P * R 0 R 1基团时，R 0是甲基; 并且R 1是C-键合的光学富集或光学纯的手性，单或多环，非芳族烃或杂烃基，其具有3至12个环原子和1至4个环，并且其具有立体碳原子至少在 P-C键; 这些配体的金属络合物是用于不对称加成反应的均相催化剂，特别是氢化。

公开(公告)号：US08450501B2

公开(公告)日：2013-05-28

申请号：US12734696

申请日：2008-11-14

申请人： Benoît Pugin ,  Matthias Lotz ,  Heidi Landert ,  Adrian Wyss ,  Raphael Aardoom ,  Björn Gschwend ,  Andreas Pfaltz ,  Felix Spindler

发明人： Benoît Pugin ,  Matthias Lotz ,  Heidi Landert ,  Adrian Wyss ,  Raphael Aardoom ,  Björn Gschwend ,  Andreas Pfaltz ,  Felix Spindler

IPC分类号： C07D333/26

CPC分类号： C07F13/005 ,  B01J31/1875 ,  B01J31/2291 ,  B01J31/2495 ,  B01J2231/643 ,  B01J2231/645 ,  B01J2531/0238 ,  B01J2531/822 ,  B01J2531/827 ,  C07B53/00 ,  C07B2200/07 ,  C07C67/303 ,  C07C67/31 ,  C07C231/12 ,  C07C231/18 ,  C07F9/46 ,  C07F9/5004 ,  C07F9/5018 ,  C07F9/5022 ,  C07F9/5027 ,  C07F9/65515 ,  C07F9/65517 ,  C07F9/65522 ,  C07F9/655354 ,  C07F17/02 ,  C07C69/34 ,  C07C69/732 ,  C07C69/675 ,  C07C233/47

摘要： Compounds of the formula (I), in the form of mixtures comprising predominantly one diastereomer or in the form of pure diastereomers, Z1-Q-P*R0R1 (I) in which Z1 is a C-bonded, secondary phosphine group —P(R)2; in which R is in each case independently hydrocarbon radicals or heterohydrocarbon radicals, or Z1 is the —P*R0R1 group; Q is a bivalent, achiral, aromatic base skeleton, a bivalent, achiral ferrocene base skeleton, an optionally substituted bivalent cycloalkane or heterocycloalkane skeleton, or a C1-C4-alkylene skeleton.

摘要翻译： 主要为一种非对映体或纯非对映体形式的混合物形式的式（I）化合物，其中Z 1为C键，仲膦基-P（R）的Z1-QP * R0R1（I） 2; 其中R各自独立地为烃基或杂烃基，或Z1为-P * R0R1基团; Q是二价，非手性芳族基骨架，二价，非手性二茂铁基骨架，任选取代的二价环烷烃或杂环烷骨架，或C 1 -C 4亚烷基骨架。

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：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：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

公开(公告)号：US20080287698A1

公开(公告)日：2008-11-20

申请号：US11579692

申请日：2005-05-03

申请人： Matthias Lotz ,  Felix Spindler

发明人： Matthias Lotz ,  Felix Spindler

IPC分类号： C07F17/00

CPC分类号： C07C231/18 ,  B01J31/2295 ,  B01J31/2409 ,  B01J31/2433 ,  B01J31/2438 ,  B01J2231/643 ,  B01J2231/645 ,  B01J2531/0286 ,  B01J2531/821 ,  B01J2531/822 ,  B01J2531/827 ,  C07B2200/07 ,  C07C51/36 ,  C07C67/303 ,  C07C67/31 ,  C07C213/02 ,  C07F17/02 ,  C07C57/30 ,  C07C69/34 ,  C07C69/732 ,  C07C69/675 ,  C07C217/08 ,  C07C233/47

摘要： Compounds of the formula (I) or (I′), where R1 is a hydrogen atom or C1-C4-alkyl and R′1 is C1-C4-alkyl; X1 and X2 are each, independently of one another, a secondary phosphine group; R2 is hydrogen, R01R02R03Si—, C1-C18acyl substituted by halogen, hydroxy, C1-C8-alkoxy or R04R05N—, -or 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-oxapcntylene; 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 C6-C20-arylene; v is 0 or an integer from 1 to 4; and * denotes a mixture of racemic or enantiomerically pure diastereomers or pure racemic or enantiomerically diastereomers, are excellent chiral ligands for metal complexes as enantioselective catalysts for the hydrogenation of prochiral organic compounds.

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：US07671225B2

公开(公告)日：2010-03-02

申请号：US11579692

申请日：2005-05-03

申请人： Matthias Lotz ,  Felix Spindler

发明人： Matthias Lotz ,  Felix Spindler

IPC分类号： C07F19/00 ,  C07F17/02

CPC分类号： C07C231/18 ,  B01J31/2295 ,  B01J31/2409 ,  B01J31/2433 ,  B01J31/2438 ,  B01J2231/643 ,  B01J2231/645 ,  B01J2531/0286 ,  B01J2531/821 ,  B01J2531/822 ,  B01J2531/827 ,  C07B2200/07 ,  C07C51/36 ,  C07C67/303 ,  C07C67/31 ,  C07C213/02 ,  C07F17/02 ,  C07C57/30 ,  C07C69/34 ,  C07C69/732 ,  C07C69/675 ,  C07C217/08 ,  C07C233/47

摘要： Compounds of the formula (I) or (I′), where R1 is a hydrogen atom or C1-C4-alkyl and R′1 is C1-C4-alkyl; X1 and X2 are each, independently of one another, a secondary phosphine group; R2 is hydrogen, R01R02R03Si—, C1-C18.acyl substituted by halogen, hydroxy, C1-C8-alkoxy or R04R05N—, -or 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-oxapcntylene; 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 C6-C20-arylene; v is 0 or an integer from 1 to 4; and * denotes a mixture of racemic or enantiomerically pure diastereomers or pure racemic or enantiomerically diastereomers, 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R 1是氢原子或C 1 -C 4 - 烷基，R'1是C 1 -C 4烷基; X1和X2各自独立地为次膦基; R2是氢，被卤素，羟基，C1-C8-烷氧基或R04R05N-取代的C1-C18烷基酰基，或 - 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 氧亚麻 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 6 -C 20亚芳基; v为0或1至4的整数; 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异构体非对映体的混合物，作为用于前手性有机化合物氢化的对映选择性催化剂的金属络合物的优异手性配体。

公开(公告)号：US20070142655A1

公开(公告)日：2007-06-21

申请号：US10582406

申请日：2004-12-10

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

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

IPC分类号： C07F17/02

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。