齐岳-四氟硼酸三叔丁基膦/三环己基膦/三环己基膦四氟硼酸盐/1,2-双(二苯基膦)乙烷/丙烷
齐岳-四氟硼酸三叔丁基膦/三环己基膦/三环己基膦四氟硼酸盐/1,2-双(二苯基膦)乙烷/丙烷
膦配体应用
不对称催化发展至今,手性配体的设计与合成仍然是不对称催化研究的中心。目前成熟的手性单膦配体通常集中在联芳基、螺环、二茂铁、TADDOL等骨架上,结构新颖、简捷易得的配体仍然有待于开发。通过对氮杂和氧杂苯并降冰片烯的不对称膦氢化反应,我们直接以高产率高对映选择性获得了一些列氮杂单膦配体(Azaphos)和氧杂单膦配体(Oxaphos)。随后,我们尝试了它们不对称催化中的应用,目前Oxaphos已经在Ru催化的醛的芳基化反应中表现出良好的催化活性和手性控制。
烯烃的不对称膦氢化加成反应不仅原子经济,而且可以直接有效的构建光学活性膦化合物。在本文中,我们报道了氮杂、氧杂双环苯并二烯与二芳基膦的不对称膦氢化反应,提供了一种直接有效的获得手性叔膦的方法(高达99%产率,高达99% ee)。特别值得注意的是,所得到的手性膦产物已经作为配体应用于Ru催化的醛与芳基硼酸的不对称加成反应,这显示了它们作为配体的巨大潜力。该方法通过底物和二芳基膦的变化就可以获得一些列含有桥环骨架的单膦配体Azaphos和Oxaphos,同时所得的该配体骨架还能和其他优势配体骨架对接组装,优化配体结构,进一步形成新的优势配体。
手性膦配体在不同类型过渡金属催化的不对称合成中发挥着重要作用,在20世纪70年代初为铑催化的不对称氢化开发了CAMP和DIPAMP配体以来,P-手性膦配体的发展一直很缓慢。直到20世纪90年代后期,随着bisP*、TangPhos等配体的出现,P-手性膦配体的开发才重新受到关注。
直至今日,有机合成化学家相继开发了许多手性膦配体,为不对称催化作出了突破性的贡献。但是,大多数P-手性膦配体都存在制备难度大、操作不方便或反应活性和选择性差的问题,导致它们的应用十分有限,只有少数配体可用,如DIPAMP、bisP*、TangPhos、DuanPhos和QuinoxP等(Figure 1)。所以,寻求新颖、高效和实用的手性膦配体一直是有机合成化学家关注的焦点。
13716-12-6
"Tri-Tert-Butylphosphine 三叔丁基膦"
Solution In Toluene, SpcSeal
"Tri-Tert-Butylphosphine 三叔丁基膦"
10% In Pentane, SpcSeal
"Tri-Tert-Butylphosphine 三叔丁基膦"
20%(1M) Solution In Toluene, SpcSeal
"Tri-Tert-Butylphosphine 三叔丁基膦"
"95% Tri-Tert-Butylphosphine 三叔丁基膦"
10% Solution In Hexanes,SpcSeal
"Tri-Tert-Butylphosphine 三叔丁基膦"
30% Solution In Toluene, SpcSeal
"Tri-Tert-Butylphosphine 三叔丁基膦"
10% Solution In Toluene, SpcSeal
"Tri-Tert-Butylphosphine 三叔丁基膦"
"三叔丁基膦(1.0mol甲苯溶液)"
"Tri-Tert-Butylphosphine三叔丁基膦"
6476-36-4
Triisopropylphosphine 三异丙基膦
607-01-2
Ethyldiphenylphosphine
1605-53-4
Diethylphenylphosphine 二乙基苯膦
7650-84-2
Diphenyl-N-Propylphosphine 二苯基丙基膦
2234-97-1
"Tri-N-Propylphosphine 三正丙基磷化氢"
4731-53-7
"Trioctylphosphine 三辛基膦"
三辛基膦
4455-77-0
"(Methoxymethyl)Diphenylphosphine Oxide ( 甲氧基甲基)二苯基磷氧"
"(METHOXYMETHYL)DIPHENYLPHOSPHINE OXIDE苹果酸(( 甲氧基甲基)二苯基磷氧)"
"Phosphine Oxide, Diphenyl(Methoxymethyl)-( 甲氧基甲基)二苯基磷氧"
15573-38-3
"Tris(Trimethylsilyl)Phosphine三(三甲硅烷基)膦"
Tris(Trimethylsilyl)Phosphine 三(三甲硅烷基)膦
6399-81-1
"Triphenylphosphine Hydrobromide 三苯基膦氢溴酸盐"
Triphenylphosphine Hydrobromide三苯基膦氢溴酸盐
62336-24-7
"2-Bromophenyldiphenylphosphine"
6372-42-5
"Phosphine, Cyclohexyldiphenyl- 环己基二苯基磷"
二苯基环己基膦
14180-51-9
Bis(4-Methoxyphenyl)Phenylphosphine 双(4-甲氧基苯基)苯基膦
32673-25-9
Di-Tert-Butylphenylphosphine 二叔丁基苯基膦
1259-35-4
Tris(Pentafluorophenyl)Phosphine
5518-52-5
"Tri(2-Furyl)Phosphine三(2-呋喃基)磷化氢"
三(2-呋喃)磷化氢
137348-86-8
"Bis(Tert-Butyl) N,N-Bis(Isopropyl)PhosphoramiditeN,N-二异丙基亚磷酰胺二叔丁酯"
739-58-2
"4-(Dimethylamino)Phenyldiphenylphosphine4-(二甲氨基)苯基二苯基磷"
"Diphenyl[4-(N,N-Dimethylamino)Phenyl]Phosphine"
37943-90-1
Diphenyl-2-Pyridylphosphine 二苯基-2-吡啶膦
85417-41-0
Tris(2,6-Dimethoxyphenyl)Phosphine 三(2,6-二甲氧基苯)膦
7650-88-6
"Tricyclopentylphosphine 三环戊基膦"
"(S)-(-)-2,2'-Bis(Di-P-Tolylphosphino)-1,1'-Binaphthyl(S)-(-)-2,2'-双(二-4-甲基苯基膦)-1,1'-联萘双二苯基磷酰联萘"
2129-31-9
"4-(Diphenylphosphino)Benzoic Acid"
17261-28-8
"2-(Diphenylphosphino)Benzoic Acid 2-(二苯基膦基)苯甲酸"
"2-(DIPHENYLPHOSPHINO)BENZOIC ACID2-二苯基膦苯甲酸"
99646-28-3
"(R)-(+)-2,2'-Bis(Di-P-Tolylphosphino)-1,1'-Binaphthyl (R)-(+)-2,2'-联[二-(4-甲基苯基)膦基]-1,1'-联萘"
6002-40-0
"Di-T-Butylmethylphosphine"
224311-51-7
"2-(Di-T-Butylphosphino)Biphenyl 2-(二叔丁基膦)联苯"
"2-(Di-Tert-Butylphosphino)Biphenyl2-(二叔丁基膦基)联苯"
"JohnPhos2-(二叔丁基膦)联苯"
247940-06-3
"2-(Dicyclohexylphosphino)Biphenyl CyJohnPhos"
"2-(Dicyclohexylphosphino)Biphenyl2-(二环己基膦基)联苯"
"2-(Dicyclohexylphosphino)Biphenyl2-(二环己基膦基)联苯"
213697-53-1
2-Dicyclohexylphosphino-2'-(N,N-Dimethylamino)Biphenyl 2-二环己膦基-2'-(N,N-二甲胺)-联苯
"2-Dicyclohexylphosphino-2'-(N,N-Dimethylamino)Biphenyl2-二环己膦基-2’-(N,N-二甲胺)-联苯"
"DavePhos2-二环己膦基-2′-(N,N-二甲胺)联苯"
434336-16-0
"Bis(2-Dicyclohexylphosphinophenyl)Ether 双(二环己基膦基苯基)醚"
255836-67-0
"Rac-2-(Di-T-Butylphosphino)-1,1-Binaphthyl2-(二叔丁基磷)-1,1’-联萘"
251320-86-2
"MePhos 2-二环己基磷-2'-甲基联苯251320-86-2 /"
"2-(Dicyclohexylphosphino)-2'-Methylbiphenyl2-二环己基磷-2’-甲基联苯"
240417-00-9
"2-Diphenylphosphino-2'-(N,N-Dimethylamino)Biphenyl 2-(二苯基膦)-2'-(N,N-二甲基氨基)联苯"
93634-87-8
"Tert-Butyldicyclohexylphosphine 叔丁基二环己基膦"
"T-Butyldicyclohexylphosphine"
436865-11-1
"Di-Tert-Butyl(Cyclohexyl)Phosphine 二-叔-丁基(环己基)磷"
10wt% Solution In Hexanes, SpcSeal
Di-Tert-Butylcyclohexylphosphine 环己基二叔丁基膦
312959-24-3
"1,2,3,4,5-Pentaphenyl-1'-(Di-Tert-Butylphosphino)Ferrocene 1,2,3,4,5-五苯基-1'-(二叔丁基膦)二茂铁"
33494-80-3
"磷酸二叔丁酯钾盐"
479094-62-7
"二叔丁基甲基膦四氟硼酸盐"
58656-04-5
"Tricyclohexylphosphonium Tetrafluoroborate 三环己基膦四氟硼酸盐"
"TRICYCLOHEXYLPHOSPHONIUM TETRAFLUOROBORATE三环己基膦四氟硼酸盐"
"Tricyclohexylphosphonium TetrafluoroborateTricyclohexylphosphonium Tetrafluoroborate"
564483-18-7
2-(Dicyclohexylphosphino)-2',4',6'-Tri-I-Propyl-1,1'-Biphenyl 2-二环己基磷-2',4',6'-三异丙基联苯
"X-PHOS2-二环己基磷-2,4,6-三异丙基联苯"
"X-Phos, ChemDose™ Tablets2-二环己基磷-2',4',6'-三异丙基联苯"
113978-91-9
"Tributylphosphine Tetrafluoroborate四氟硼酸三正丁基磷"
321921-71-5
"Di(1-Adamantyl)-N-Butylphosphine正丁基二(1-金刚烷基)膦"
"Butyldi-1-Adamantylphosphine"
"Butyldi-1-Adamantylphosphine正丁基二(1-金刚烷基)膦"
657408-07-6
"2-Dicyclohexylphosphino-2',6'-Dimethoxy-1,1'-Biphenyl Sphos"
"2-Dicyclohexylphosphino-2',6'-Dimethoxybiphenyl2-双环己基膦-2’,6’-二甲氧基联苯"
"Dicyclohexyl({2-[(2,6-Dimethoxyphenyl)Methyl]Phenyl}Methyl)Phosphane 2-双环己基膦-2',6'-二甲氧基联苯"
Dicyclohexyl({2-[(2,6-Dimethoxyphenyl)Methyl]Phenyl}Methyl)Phosphane 2-双环己基膦-2',6'-二甲氧基联苯