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    • 10. 发明公开
    • ENANTIOSELECTIVE PHOSPHORAMIDITE COMPOUNDS AND CATALYSTS
    • 对流式亚磷酸盐化合物及催化剂
    • EP1745056A2
    • 2007-01-24
    • EP05778948.9
    • 2005-04-29
    • Yale University Corporation
    • HARTWIG, John, F.LEITNER, AndreasSHU, Chutian
    • C07F9/22B01J31/18
    • C07D295/023B01J31/186B01J2231/348B01J2231/44B01J2231/645B01J2531/16B01J2531/17B01J2531/64B01J2531/66B01J2531/821B01J2531/822B01J2531/824B01J2531/827B01J2531/828B01J2531/847C07B53/00C07C209/60C07C213/08C07C319/20C07F9/2466C07F9/657154C07C211/28C07C211/45C07C217/58C07C323/36
    • 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; R1 and R2 are independently an optionally substituted C1-12 alkyl group, an optionally substituted (CH2)n-aromatic group or (CH2)n-heteroaromatic group, or are linked together to form an optionally substituted aliphatic or (CH2)n-aromatic dianion of a diol, diamine, dithiol, aminoalcohol, aminohiolate or a alcoholthiol group; R3’ and R3 are each independently H, an optionally substituted C1-C12 alkyl group or an optionally substituted (CH2)n-aromatic group with the proviso that R3’ and R3 are not both H, or together R3’ and R3 form an optionally substituted C5-C15 saturated or unsaturated carbocyclic ring; R4 is H, an optionally substituted C1-C12 alkyl group or an optionally substituted (CH2)n-aromatic group; R5 is absent, H, an optionally substituted C1-C12 alkyl group or an optionally substituted (CH2)n-aromatic or (CH2)n-heteroaromatic group; Ra and Ra’ are each independently H or a C1-C3 alkyl group, or Ra and Ra’ together with the carbon to which they are attached form a optionally substituted C5-C15 saturated or unsaturated carbocyclic or heterocyclic ring, or an aromatic or heteroaromatic ring; R6 and R7 are each independently H, an optionally substituted C1-C12 alkyl group or an optionally substituted (CH2)n-aromatic group, with the proviso that R5, R6 and R7 cannot simultaneously be H, and when Ra and Ra’, together with the carbon to which they are attached, form a carbocyclic ring, heterocyclic ring or an aromatic or heteroaromatic ring, R5 is absent or is preferably H; R6 and R7 are preferably H or CH3; 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.
    • 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,包括加氢胺化反应,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,本发明涉及根据通用结构(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独立地为任选取代的C 1-12烷基,任选取代的(CH 2)n - 芳族基团或(CH 2)n - 杂芳族基团,或者连接在一起形成任选取代的脂族或(CH 2)n - 芳族 二醇,二胺,二硫醇,氨基醇,氨基硫醇盐或醇硫醇基的二价阴离子; 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)n - 芳基,条件是R 3'和R 3不都是H,或一起R 3' 取代的C5-C15饱和或不饱和碳环; R4为H,任选取代的C1-C12烷基或任选取代的(CH2)n-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)n - 芳族或(CH 2)n - 杂芳族基团; Ra和Ra'各自独立地为H或C1-C3烷基,或者Ra和Ra'与它们所连接的碳一起形成任选取代的C5-C15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)n - 芳族基团,条件是R 5,R 6和R 7不能同时为H,并且当Ra和Ra' 与它们所连接的碳形成碳环,杂环或芳族或杂芳族环,R5不存在或优选为H; R6和R7优选为H或CH3; 并且每个n独立地为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。