CN105153229A - 一种手性三齿pnn配体及其在不对称氢化反应中的应用 - Google Patents
一种手性三齿pnn配体及其在不对称氢化反应中的应用 Download PDFInfo
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- CN105153229A CN105153229A CN201510340214.8A CN201510340214A CN105153229A CN 105153229 A CN105153229 A CN 105153229A CN 201510340214 A CN201510340214 A CN 201510340214A CN 105153229 A CN105153229 A CN 105153229A
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- Prior art keywords
- reaction
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- ligand
- diphosphine
- acac
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- 239000003446 ligand Substances 0.000 title claims abstract description 45
- 238000009876 asymmetric hydrogenation reaction Methods 0.000 title abstract description 25
- 238000006243 chemical reaction Methods 0.000 claims abstract description 43
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 17
- 238000003786 synthesis reaction Methods 0.000 claims abstract description 17
- 238000005984 hydrogenation reaction Methods 0.000 claims abstract description 9
- ZEUITGRIYCTCEM-KRWDZBQOSA-N (S)-duloxetine Chemical compound C1([C@@H](OC=2C3=CC=CC=C3C=CC=2)CCNC)=CC=CS1 ZEUITGRIYCTCEM-KRWDZBQOSA-N 0.000 claims abstract description 4
- VHGCDTVCOLNTBX-QGZVFWFLSA-N atomoxetine Chemical compound O([C@H](CCNC)C=1C=CC=CC=1)C1=CC=CC=C1C VHGCDTVCOLNTBX-QGZVFWFLSA-N 0.000 claims abstract description 4
- 229960002430 atomoxetine Drugs 0.000 claims abstract description 4
- 229960002866 duloxetine Drugs 0.000 claims abstract description 4
- 229910052741 iridium Inorganic materials 0.000 claims abstract description 4
- VURFVHCLMJOLKN-UHFFFAOYSA-N diphosphane Chemical compound PP VURFVHCLMJOLKN-UHFFFAOYSA-N 0.000 claims description 28
- 239000001257 hydrogen Substances 0.000 claims description 16
- 229910052739 hydrogen Inorganic materials 0.000 claims description 16
- 238000006555 catalytic reaction Methods 0.000 claims description 15
- 239000002904 solvent Substances 0.000 claims description 13
- XQJHRCVXRAJIDY-UHFFFAOYSA-N aminophosphine Chemical compound PN XQJHRCVXRAJIDY-UHFFFAOYSA-N 0.000 claims description 9
- 125000003118 aryl group Chemical group 0.000 claims description 9
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- 150000003624 transition metals Chemical class 0.000 claims description 8
- 150000002431 hydrogen Chemical class 0.000 claims description 7
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- 125000000217 alkyl group Chemical group 0.000 claims description 5
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- VNNDVNZCGCCIPA-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;manganese Chemical compound [Mn].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O VNNDVNZCGCCIPA-FDGPNNRMSA-N 0.000 claims description 2
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- ATALOFNDEOCMKK-OITMNORJSA-N aprepitant Chemical compound O([C@@H]([C@@H]1C=2C=CC(F)=CC=2)O[C@H](C)C=2C=C(C=C(C=2)C(F)(F)F)C(F)(F)F)CCN1CC1=NNC(=O)N1 ATALOFNDEOCMKK-OITMNORJSA-N 0.000 claims description 2
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- 150000004945 aromatic hydrocarbons Chemical class 0.000 claims description 2
- GGRQQHADVSXBQN-FGSKAQBVSA-N carbon monoxide;(z)-4-hydroxypent-3-en-2-one;rhodium Chemical compound [Rh].[O+]#[C-].[O+]#[C-].C\C(O)=C\C(C)=O GGRQQHADVSXBQN-FGSKAQBVSA-N 0.000 claims description 2
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- BMGNSKKZFQMGDH-FDGPNNRMSA-L nickel(2+);(z)-4-oxopent-2-en-2-olate Chemical compound [Ni+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O BMGNSKKZFQMGDH-FDGPNNRMSA-L 0.000 claims description 2
- HFPZCAJZSCWRBC-UHFFFAOYSA-N p-cymene Chemical compound CC(C)C1=CC=C(C)C=C1 HFPZCAJZSCWRBC-UHFFFAOYSA-N 0.000 claims description 2
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- 238000007363 ring formation reaction Methods 0.000 claims description 2
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- 238000006276 transfer reaction Methods 0.000 claims description 2
- 229910052720 vanadium Inorganic materials 0.000 claims description 2
- 125000002485 formyl group Chemical group [H]C(*)=O 0.000 claims 1
- 238000005930 hydroaminomethylation reaction Methods 0.000 claims 1
- 230000000640 hydroxylating effect Effects 0.000 claims 1
- -1 imine salts Chemical class 0.000 abstract description 10
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- 229940067107 phenylethyl alcohol Drugs 0.000 abstract description 5
- IMSODMZESSGVBE-UHFFFAOYSA-N 2-Oxazoline Chemical compound C1CN=CO1 IMSODMZESSGVBE-UHFFFAOYSA-N 0.000 abstract description 4
- ZWVHTXAYIKBMEE-UHFFFAOYSA-N 2-hydroxyacetophenone Chemical compound OCC(=O)C1=CC=CC=C1 ZWVHTXAYIKBMEE-UHFFFAOYSA-N 0.000 abstract description 4
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- 238000004519 manufacturing process Methods 0.000 abstract description 3
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- KUXDQQMEFBFTGX-UHFFFAOYSA-N [N].P Chemical compound [N].P KUXDQQMEFBFTGX-UHFFFAOYSA-N 0.000 abstract 2
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