催化学报
催化學報
최화학보
CHINESE JOURNAL OF CATALYSIS
2015年
1期
93-99
,共7页
丙酮%不对称催化%七元环状亚胺%Mannich反应%有机催化
丙酮%不對稱催化%七元環狀亞胺%Mannich反應%有機催化
병동%불대칭최화%칠원배상아알%Mannich반응%유궤최화
Acetone%Asymmetric catalysis%Seven-membered cyclic imine%Mannich reaction%Organocatalysis
用脯氨酸作为催化剂,研究了各种取代的二苯并1,4-氧氮杂卓衍生物类七元环状亚胺和丙酮的直接Mannich反应,该反应能高对映选择得到一系列旋光活性的含有β羰基的七元环状氮杂环化合物(93%–98%ee)。用丁酮作为Mannich给体时,能得到专一的区域选择性和96%–97%ee的产物。进一步通过X射线单晶衍射分析其中一个产物的衍生物,确定了产物手性中心绝对构型为R,其它同类型产物绝对构型随后通过化学类比方法推断确认。
用脯氨痠作為催化劑,研究瞭各種取代的二苯併1,4-氧氮雜卓衍生物類七元環狀亞胺和丙酮的直接Mannich反應,該反應能高對映選擇得到一繫列鏇光活性的含有β羰基的七元環狀氮雜環化閤物(93%–98%ee)。用丁酮作為Mannich給體時,能得到專一的區域選擇性和96%–97%ee的產物。進一步通過X射線單晶衍射分析其中一箇產物的衍生物,確定瞭產物手性中心絕對構型為R,其它同類型產物絕對構型隨後通過化學類比方法推斷確認。
용포안산작위최화제,연구료각충취대적이분병1,4-양담잡탁연생물류칠원배상아알화병동적직접Mannich반응,해반응능고대영선택득도일계렬선광활성적함유β탄기적칠원배상담잡배화합물(93%–98%ee)。용정동작위Mannich급체시,능득도전일적구역선택성화96%–97%ee적산물。진일보통과X사선단정연사분석기중일개산물적연생물,학정료산물수성중심절대구형위R,기타동류형산물절대구형수후통과화학류비방법추단학인。
Various substituted dibenzo[b,f][1,4]oxazepines as seven‐membered cyclic imines underwent a highly enantioselective direct Mannich reaction with acetone when catalyzed by proline. These reactions gave a range of optically activeβ‐carbonyl seven‐membered N‐heterocycles with excellent enantioselectivity (93%–98%ee). With 2‐butanone as a Mannich donor, the single regioselective product was obtained with 96%–97%ee. The absolute configuration of the product was assigned to be R by X‐ray single crystal analysis of its derivative.
