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    • 2. 发明申请
    • PROCESS FOR THE DE-ENRICHMENT OF ENANTIOMERICALLY ENRICHED SUBSTRATES
    • 去除强化基底的方法
    • WO2006046062A1
    • 2006-05-04
    • PCT/GB2005/004179
    • 2005-10-27
    • AVECIA PHARMACEUTICALS LIMITEDBLACKER, Andrew, JohnSTIRLING, Matthew, John
    • BLACKER, Andrew, JohnSTIRLING, Matthew, John
    • C07B55/00C07B31/00C07C29/145
    • C07B55/00C07B2200/07C07C29/00C07C33/22
    • There is provided a process for the de-enrichment of enantiomerically enriched compositions which comprises reacting an enantiomerically enriched composition comprising at least a first enantiomer or diastereomer of a substrate comprising a carbon-heteroatom bond, wherein the carbon is a chiral centre and the heteroatom is a group VI heteroatom, in the presence of a catalyst system and optionally a reaction promoter to give a product composition comprising first and second enantiomers or diastereomers of the substrate having a carbon-heteroatom bond, the ratio of second to first enantiomer or disatereomer in the product composition being greater than the ratio of second to first enantiomer or disatereomer in the enantiomerically enriched composition. Preferred substrates include compounds of Formula (1) wherein: X represents O, S; R 1 , R 2 each independently represents an optionally substituted hydrocarbyl, a perhalogenated hydrocarbyl, an optionally substituted heterocyclyl group; or R 1 & R 2 are optionally linked in such a way as to form an optionally substituted ring(s); provided that R 1 and R 2 are selected such that * is a chiral centre. In a preferred process a compound of Formula : (2) wherein: X represents O, S; R 1 , R 2 each independently represents an optionally substituted hydrocarbyl, a perhalogenated hydrocarbyl, an optionally substituted heterocyclyl group; or R 1 & R 2 are optionally linked in such a way as to form an optionally substituted ring(s); provided that R1 and R2 are different, may be obtained.
    • 提供了对富含对映体的组合物进行去富集的方法,该方法包括使包含至少第一对映异构体或包含碳 - 杂原子键的底物的非对映异构体的对映异构体富集的组合物反应,其中碳是手性中心,杂原子是 VI族杂原子,在催化剂体系和任选的反应促进剂的存在下,得到包含具有碳 - 杂原子键的底物的第一和第二对映异构体或非对映异构体的产物组合物,第二对映异构体或二聚异构体的比例 产物组成大于对映异构体富集组合物中第二至第一对映异构体或二聚异构体的比例。 优选的底物包括式(1)的化合物,其中:X表示O,S; R 1,R 2各自独立地表示任选取代的烃基,全卤代烃基,任选取代的杂环基; 或R 1和R 2任选地以使得形成任选取代的环的方式连接; 条件是选择R 1和R 2以使得*是手性中心。 在优选的方法中,式(2)的化合物其中:X表示O,S; R 1,R 2各自独立地表示任选取代的烃基,全卤代烃基,任选取代的杂环基; 或R 1和R 2任选地以使得形成任选取代的环的方式连接; 只要R1和R2不同,就可以得到。
    • 3. 发明申请
    • CATALYST COMPOSITIONS AND THEIR USE IN THE DE-ENRICHMENT OF ENANTIOMERICALLY ENRICHED SUBSTRATES
    • 催化剂组合物及其在完全充分增强底物中的应用
    • WO2006046059A1
    • 2006-05-04
    • PCT/GB2005/004176
    • 2005-10-27
    • AVECIA PHARMACEUTICALS LIMITEDBLACKER, Andrew, JohnSTIRLING, Matthew, John
    • BLACKER, Andrew, JohnSTIRLING, Matthew, John
    • C07B55/00
    • C07B55/00
    • There is provided a process for the de-enrichment of enantiomerically enriched compositions which comprises reacting an enantiomerically enriched composition comprising at least a first enantiomer or diastereomer of a substrate comprising a carbon-heteroatom bond, wherein the carbon is a chiral centre and the heteroatom is a group V heteroatom, in the presence of a catalyst system and optionally a reaction promoter to give a product composition comprising first and second enantiomers or diastereomers of the substrate having a carbon-heteroatom bond, the ratio of second to first enantiomer or disatereomer in the product composition being greater than the ratio of second to first enantiomer or disatereomer in the enantiomerically enriched composition. Preferred catalyst systems include transition metal halide complex of the formula M n X p Y r wherein M is a transition metal; X is a halide; Y is a neutral optionally substituted hydrocarbyl complexing group, a neutral optionally substituted perhalogenated hydrocarbyl complexing group, or an optionally substituted cyclopentadienyl complexing group; and n, p and r are integers. The reaction promoter is preferably a halide salt.
    • 提供了对富含对映体的组合物进行去富集的方法,该方法包括使包含至少第一对映异构体或包含碳 - 杂原子键的底物的非对映异构体的对映异构体富集的组合物反应,其中碳是手性中心,杂原子是 V族杂原子,在催化剂体系和任选的反应促进剂的存在下,得到包含具有碳 - 杂原子键的基材的第一和第二对映异构体或非对映异构体的产物组合物,第二对映异构体或二聚异构体的比例在 产物组成大于对映异构体富集组合物中第二至第一对映异构体或二聚异构体的比例。 优选的催化剂体系包括式M的过渡金属卤化物络合物,其中M是过渡金属; X是卤化物; Y是中性任选取代的烃基络合基团,中性任选取代的全卤代烃基络合基团或任选取代的环戊二烯基络合基团; 并且n,p和r是整数。 反应促进剂优选为卤化物盐。
    • 7. 发明申请
    • PROCESS FOR THE TRANSFER HYDROGENATION OF AN ORGANIC COMPOUND IN THE PRESENCE OF A CATALYST REGENERATOR
    • 有机化合物在催化剂再生器存在下的转移加氢方法
    • WO2006046056A1
    • 2006-05-04
    • PCT/GB2005/004171
    • 2005-10-27
    • AVECIA PHARMACEUTICALS LIMITEDHODGES, George, RobertSTIRLING, Matthew, John
    • HODGES, George, RobertSTIRLING, Matthew, John
    • C07B31/00C07C29/145
    • C07C29/143C07B31/00Y02P20/584C07C33/22C07C33/46
    • There is provided a process for the transfer hydrogenation of an organic compound having a carbon-carbon or carbon-heteroatom double bond wherein an organic compound of formula (I): wherein: X represents CR 3 R 4 , NR 5 , (NR 5 R 6 ) + Q - , O or S; Q - represents an anion; R 1 , R 2 each independently represents an optionally substituted hydrocarbyl, a perhalogenated hydrocarbyl or an optionally substituted heterocyclyl group; R 3 , R 4 , and R 6 each independently represents a hydrogen atom, an optionally substituted hydrocarbyl, a perhalogenated hydrocarbyl or an optionally substituted heterocyclyl group; R 5 independently represents a hydrogen atom, an optionally substituted hydrocarbyl, a perhalogenated hydrocarbyl, an optionally substituted heterocyclyl group or a removable group; or one or more of R 1 & R 2 , R 1 & R 3 , R 2 & R 4 , R 3 & R 4 , R 1 & R 5 , R 2 & R 6 and R 5 & R 6 optionally being linked in such a way as to form an optionally substituted ring(s), is reacted with a hydrogen donor in the presence of a transfer hydrogenation catalyst, and substantially in the presence of a catalyst regenerator. Catalyst regenerators include oxidants, for example KMnO 4 , oxygen and oxygen/inert gas mixtures.
    • 提供了具有碳 - 碳或碳 - 杂原子双键的有机化合物的转移氢化方法,其中式(I)的有机化合物:其中:X表示CR 3 R SUP > 4 ,NR 5,(NR 5 R 6)6 - ,O或S; Q 表示阴离子; R 1,R 2各自独立地表示任选取代的烃基,全卤代烃基或任选取代的杂环基; R 3,R 4和R 6各自独立地表示氢原子,任选取代的烃基,全卤代烃基或任选取代的杂环基 组; R 5独立地表示氢原子,任选取代的烃基,全卤代烃基,任选取代的杂环基或可除去的基团; 或R 1,R 2,R 2,R 3和R 3中的一个或多个, R< 3>< 4>,< 1>< 5> 任选地在这样的一个或多个连接在一起的第二个和第六个和第六个和第六个和第六个 在形成任选取代的环的方式与氢供体在转移氢化催化剂的存在下,基本上在催化剂再生器的存在下反应。 催化剂再生器包括氧化剂,例如KMnO 4,氧和氧/惰性气体混合物。