Abstract:
This invention relates to phosphoramidite compounds and catalyst complexes which can be used to provide enantioselective reactions including hydroamination reactions, etherification reactions and conjugate addition reactions and allylic substitution reactions, among others. In a first aspect, the present invention is directed to phosphoramidite and related compounds according to general structure (I), where Z is absent or is a group containing O, N or S, preferably O; R 1 and R 2 are independently an optionally substituted C 1-12 alkyl group, an optionally substituted (CH 2 ) n -aromatic group or (CH 2 ) n -heteroaromatic group, or are linked together to form an optionally substituted aliphatic or (CH 2 ) n -aromatic dianion of a diol, diamine, dithiol, aminoalcohol, aminohiolate or a alcoholthiol group; R 3' and R 3 are each independently H, an optionally substituted C 1 -C 12 alkyl group or an optionally substituted (CH 2 ) n -aromatic group with the proviso that R 3' and R 3 are not both H, or together R 3' and R 3 form an optionally substituted C 5 -C 15 saturated or unsaturated carbocyclic ring; R 4 is H, an optionally substituted C 1 -C 12 alkyl group or an optionally substituted (CH 2 ) n -aromatic group; R 5 is absent, H, an optionally substituted C 1 -C 12 alkyl group or an optionally substituted (CH 2 ) n -aromatic or (CH 2 ) n -heteroaromatic group; R a and R a' are each independently H or a C 1 -C 3 alkyl group, or R a and R a' together with the carbon to which they are attached form a optionally substituted C 5 -C 15 saturated or unsaturated carbocyclic or heterocyclic ring, or an aromatic or heteroaromatic ring; R 6 and R 7 are each independently H, an optionally substituted C 1 -C 12 alkyl group or an optionally substituted (CH 2 ) n -aromatic group, with the proviso that R 5 , R 6 and R 7 cannot simultaneously be H, and when R a and R a' , together with the carbon to which they are attached, form a carbocyclic ring, heterocyclic ring or an aromatic or heteroaromatic ring, R 5 is absent or is preferably H; R 6 and R 7 are preferably H or CH 3 ; and each n is independently 0, 1, 2, 3, 4, 5 or 6 and wherein at least one of the carbon atoms attached to the nitrogen of the phosphoramidite group is a chiral center.
Abstract translation:本发明涉及可用于提供对映选择性反应的亚磷酰胺化合物和催化剂配合物,包括水解反应,醚化反应和共轭加成反应以及烯丙基取代反应等。 在第一方面,本发明涉及根据通式(I)的亚磷酰胺和相关化合物,其中Z不存在或是含有O,N或S,优选O的基团; R 1和R 2独立地是任选取代的C 1-12烷基,任选取代的(CH 2)2 N 或芳族基团,或连接在一起形成任选取代的脂族基或(CH(CH 2)n) - 杂芳基或(CH 2) 二醇,二胺,二硫醇,氨基醇,氨基硫醇或醇硫醇基的二芳基二阴离子; R 3'和R 3'各自独立地为H,任选取代的C 1 -C 12烷基或 任选取代的(CH 2)2 - 芳基,条件是R 3'和R 3'是 不是H或一起R 3'和R 3'形成任选取代的C 5 -C 15饱和的 或不饱和碳环; R 4是H,任选取代的C 1 -C 12烷基或任选取代的(CH 2)2 - ) u> 芳基; R 5不存在,H,任选取代的C 1 -C 12烷基或任选取代的(CH 2 CH 2) - 芳族或(CH 2)2 - 亚芳基; R a a和R a a'各自独立地为H或C 1 -C 3烷基,或R 与它们所连接的碳一起形成任选取代的C 5 -C 15亚烷基 饱和或不饱和的碳环或杂环,或芳族或杂芳族环; R 6和R 7各自独立地为H,任选取代的C 1 -C 12烷基或 任选取代的(CH 2)2 - 芳基,条件是R 5,R 6和R 4 7不能同时为H,当R a a和R a a'与它们所连接的碳一起形成碳环时, ,杂环或芳族或杂芳族环,R 5不存在或优选为H; R 6和R 7优选为H或CH 3; 并且每个n独立地是0,1,2,3,4,5或6,并且其中连接到亚磷酰胺基团的氮上的至少一个碳原子是手性中心。
Abstract:
Verfahren zur Isomerisierung von cis-2-Pentennitril zu 3-Pentennitrilen, indem man cis-2-Pentennitril mit Amidinen, tertiären Aminen oder deren Gemischen als Katalysator bei Temperaturen von 80 bis 200°C und einem Druck von 0,01 bis 50 bar isomerisiert.
Abstract:
Verfahren zur Herstellung von Nickel(0)-Phosphorligand-Komplexen enthaltend mindestens ein Nickel(0)-Zentralatom und mindestens einen phosphorhaltigen Liganden, durch Umsetzung einer Nickel(II)-Verbindung mit einem Reduktionsmittel in Gegenwart des Liganden zu einer Reaktionsmischung, dadurch gekennzeichnet, dass a) bei der Umsetzung das Molverhältnis Reduktionsmittel : Nickel(II)-Verbindung 1 : 1 bis 1000 : 1 beträgt, gerechnet als molares Verhältnis der Redoxäquivalente, b) bei der Umsetzung das Molverhältnis phosphorhaltiger Ligand : Nickel(II)- Verbindung maximal 30 : 1 beträgt, gerechnet als molares Verhältnis P-Atome : Ni-Atome, c) in der erhaltenen Reaktionsmischung der Nickel(0)-Gehalt maximal 1,3 Gew.-% beträgt, und d) die erhaltene Reaktionsmischung extrahiert wird, indem man mindestens ein Dinitril und mindestens einen Kohlenwasserstoff zufügt, wobei sich mindestens zwei nichtmischbare Phasen bilden.
Abstract:
This invention relates to phosphoramidite compounds and catalyst complexes which can be used to provide enantioselective reactions including hydroamination reactions, etherification reactions and conjugate addition reactions and allylic substitution reactions, among others. In a first aspect, the present invention is directed to phosphoramidite and related compounds according to general structure (I), where Z is absent or is a group containing O, N or S, preferably O; R 1 and R 2 are independently an optionally substituted C 1-12 alkyl group, an optionally substituted (CH 2 ) n -aromatic group or (CH 2 ) n -heteroaromatic group, or are linked together to form an optionally substituted aliphatic or (CH 2 ) n -aromatic dianion of a diol, diamine, dithiol, aminoalcohol, aminohiolate or a alcoholthiol group; R 3’ and R 3 are each independently H, an optionally substituted C 1 -C 12 alkyl group or an optionally substituted (CH 2 ) n -aromatic group with the proviso that R 3’ and R 3 are not both H, or together R 3’ and R 3 form an optionally substituted C 5 -C 15 saturated or unsaturated carbocyclic ring; R 4 is H, an optionally substituted C 1 -C 12 alkyl group or an optionally substituted (CH 2 ) n -aromatic group; R 5 is absent, H, an optionally substituted C 1 -C 12 alkyl group or an optionally substituted (CH 2 ) n -aromatic or (CH 2 ) n -heteroaromatic group; R a and R a’ are each independently H or a C 1 -C 3 alkyl group, or R a and R a’ together with the carbon to which they are attached form a optionally substituted C 5 -C 15 saturated or unsaturated carbocyclic or heterocyclic ring, or an aromatic or heteroaromatic ring; R 6 and R 7 are each independently H, an optionally substituted C 1 -C 12 alkyl group or an optionally substituted (CH 2 ) n -aromatic group, with the proviso that R 5 , R 6 and R 7 cannot simultaneously be H, and when R a and R a’ , together with the carbon to which they are attached, form a carbocyclic ring, heterocyclic ring or an aromatic or heteroaromatic ring, R 5 is absent or is preferably H; R 6 and R 7 are preferably H or CH 3 ; and each n is independently 0, 1, 2, 3, 4, 5 or 6 and wherein at least one of the carbon atoms attached to the nitrogen of the phosphoramidite group is a chiral center.