JP2008538585A5 - - Google Patents
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- JP2008538585A5 JP2008538585A5 JP2008507990A JP2008507990A JP2008538585A5 JP 2008538585 A5 JP2008538585 A5 JP 2008538585A5 JP 2008507990 A JP2008507990 A JP 2008507990A JP 2008507990 A JP2008507990 A JP 2008507990A JP 2008538585 A5 JP2008538585 A5 JP 2008538585A5
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- reaction
- olefin
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- 238000000034 method Methods 0.000 claims description 37
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000007037 hydroformylation reaction Methods 0.000 claims description 12
- 150000001336 alkenes Chemical class 0.000 claims description 11
- 125000003118 aryl group Chemical group 0.000 claims description 7
- 125000002485 formyl group Chemical class [H]C(*)=O 0.000 claims description 7
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 claims description 7
- 229910052703 rhodium Inorganic materials 0.000 claims description 7
- 239000010948 rhodium Substances 0.000 claims description 7
- 239000004711 α-olefin Substances 0.000 claims description 7
- 125000001072 heteroaryl group Chemical group 0.000 claims description 6
- 150000002430 hydrocarbons Chemical class 0.000 claims description 5
- 125000000217 alkyl group Chemical group 0.000 claims description 4
- PPBRXRYQALVLMV-UHFFFAOYSA-N styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 claims description 4
- 125000001424 substituent group Chemical group 0.000 claims description 4
- 239000004215 Carbon black (E152) Substances 0.000 claims description 3
- 238000005669 hydrocyanation reaction Methods 0.000 claims description 3
- VBQCHPIMZGQLAZ-UHFFFAOYSA-N phosphorane Chemical compound [PH5] VBQCHPIMZGQLAZ-UHFFFAOYSA-N 0.000 claims description 3
- 125000003107 substituted aryl group Chemical group 0.000 claims description 3
- SJNALLRHIVGIBI-UHFFFAOYSA-N Allyl cyanide Chemical compound C=CCC#N SJNALLRHIVGIBI-UHFFFAOYSA-N 0.000 claims description 2
- 125000002877 alkyl aryl group Chemical group 0.000 claims description 2
- 125000003710 aryl alkyl group Chemical group 0.000 claims description 2
- 125000004429 atoms Chemical group 0.000 claims description 2
- 125000004432 carbon atoms Chemical group C* 0.000 claims description 2
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 claims description 2
- 230000027455 binding Effects 0.000 claims 8
- 239000003446 ligand Substances 0.000 claims 8
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims 3
- 229910052723 transition metal Inorganic materials 0.000 claims 3
- 150000003624 transition metals Chemical class 0.000 claims 3
- XEEYBQQBJWHFJM-UHFFFAOYSA-N iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims 2
- 239000000758 substrate Substances 0.000 claims 2
- 239000005092 Ruthenium Substances 0.000 claims 1
- 238000005917 acylation reaction Methods 0.000 claims 1
- 238000005804 alkylation reaction Methods 0.000 claims 1
- 238000005576 amination reaction Methods 0.000 claims 1
- -1 aryl Chemical class 0.000 claims 1
- 238000006254 arylation reaction Methods 0.000 claims 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N carbon Chemical group [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims 1
- 239000003054 catalyst Substances 0.000 claims 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 claims 1
- 229910052803 cobalt Inorganic materials 0.000 claims 1
- 239000010941 cobalt Substances 0.000 claims 1
- 238000006482 condensation reaction Methods 0.000 claims 1
- 238000005886 esterification reaction Methods 0.000 claims 1
- 238000011065 in-situ storage Methods 0.000 claims 1
- GKOZUEZYRPOHIO-UHFFFAOYSA-N iridium Chemical compound [Ir] GKOZUEZYRPOHIO-UHFFFAOYSA-N 0.000 claims 1
- 229910052741 iridium Inorganic materials 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 229910052759 nickel Inorganic materials 0.000 claims 1
- 238000006772 olefination reaction Methods 0.000 claims 1
- 229910052762 osmium Inorganic materials 0.000 claims 1
- SYQBFIAQOQZEGI-UHFFFAOYSA-N osmium Chemical compound [Os] SYQBFIAQOQZEGI-UHFFFAOYSA-N 0.000 claims 1
- 238000007254 oxidation reaction Methods 0.000 claims 1
- 229910052763 palladium Inorganic materials 0.000 claims 1
- XYFCBTPGUUZFHI-UHFFFAOYSA-N phosphine group Chemical group P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 claims 1
- OAICVXFJPJFONN-UHFFFAOYSA-N phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 claims 1
- 229910052698 phosphorus Inorganic materials 0.000 claims 1
- 239000011574 phosphorus Substances 0.000 claims 1
- 229910052697 platinum Inorganic materials 0.000 claims 1
- 238000006722 reduction reaction Methods 0.000 claims 1
- KJTLSVCANCCWHF-UHFFFAOYSA-N ruthenium Chemical compound [Ru] KJTLSVCANCCWHF-UHFFFAOYSA-N 0.000 claims 1
- 229910052707 ruthenium Inorganic materials 0.000 claims 1
- 238000006467 substitution reaction Methods 0.000 claims 1
- 150000001299 aldehydes Chemical class 0.000 description 5
- 150000001298 alcohols Chemical class 0.000 description 2
- 230000002452 interceptive Effects 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 150000004657 carbamic acid derivatives Chemical class 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001735 carboxylic acids Chemical class 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000005755 formation reaction Methods 0.000 description 1
- 150000004820 halides Chemical class 0.000 description 1
- 125000005842 heteroatoms Chemical group 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000003951 lactams Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 150000002825 nitriles Chemical class 0.000 description 1
Description
【００１１】
式（１）において、（ａ）Ｒはそれぞれの存在において独立して、置換アリールまたは非置換アリール、置換ヘテロアリールまたは非置換ヘテロアリール、および、ホスホラン環に結合した炭素原子において分枝したアルキルからなる群より選択され；（ｂ）ｎは１またはそれ以上の整数であり；（ｃ）点線はそれぞれの存在において任意のさらなる結合を表し、該結合によって結合されている原子が単結合、二重結合または芳香族環系の一部を形成する結合によって連結されてもよい。
【手続補正3】
【補正対象書類名】 明細書
【補正対象項目名】 ００１６
【補正方法】 変更
【補正の内容】
【００１６】
本発明の別の態様において、好ましい不斉反応はヒドロホルミル化またはヒドロシアン化のいずれかである。より好ましくは、反応はオレフィンの不斉ヒドロホルミル化であり、錯体はロジウム錯体である。そのような不斉反応では、プロキラルなオレフィンのエナンチオ選択的なヒドロホルミル化、または、エナンチオマー濃縮されたキラルなオレフィンのジアステレオ選択的なヒドロホルミル化のいずれかが引き起こされ得る。いずれの場合でも、要求される生成物のエナンチオ選択的過剰率は少なくとも６０％であり、好ましくは少なくとも８０％またはそれ以上であることが好ましい。そのようなヒドロホルミル化反応において、オレフィンは、必ずしも常にではないが、典型的には、プロキラルなα−オレフィン（すなわち、一置換された末端オレフィン）である。プロキラルなα−オレフィン（ＲＣＨ＝ＣＨ2）のヒドロホルミル化は、２つの位置異性アルデヒドの形成、すなわち、分枝型のキラルなアルデヒド（ＲＣＨ（ＣＨＯ）ＣＨ3）および直鎖型のアキラルなアルデヒド（ＲＣＨ2ＣＨ2ＣＨＯ）の形成をもたらし得る。本発明のプロセスでは、分枝型アルデヒドが主生成物であり、その結果、分枝型：直鎖型のアルデヒド生成物比が少なくとも３：１であり、好ましくは、少なくとも８：１またはそれ以上であることが望ましい。α−オレフィンにおける基Ｒは、Ｃ1〜30炭化水素（すなわち、アリール、アルキル（シクロアルキルを含む）、アラルキルまたはアルカリール）またはヘテロ原子系置換基のいずれかであり得る。Ｒが炭化水素であるとき、この炭化水素は官能基化されていなくてもよく、あるいは、１つまたは複数の非妨害性の基により官能基化されてもよい。限定されないが、そのような非妨害性の基は、アルコール、保護されたアルコール、保護されたアミン、ケトン、ニトリル、カルボン酸、エステル、ラクトン、アミド、ラクタム、カルバマート、カルボナートおよびハライドからなる群より選択され得る。Ｒがヘテロ原子系置換基であるとき、限定されないが、このような置換基は、Ｏ−アシル、Ｎ−アシルおよびＳ−アシルからなる群より選択され得る。本発明の具体的な実施形態において、α−オレフィンは、スチレン、酢酸ビニルおよびアリルシアニドからなる群より選択される。
[0011]
In formula (1), (a) R is independently in each occurrence from substituted aryl or unsubstituted aryl, substituted heteroaryl or unsubstituted heteroaryl, and alkyl branched at the carbon atom attached to the phosphorane ring. made is selected from the group; (b) n is 1 or more integer; (c) the dotted line in each occurrence represents an optional additional bond, atoms bonded by said bond is a single bond, a double forming Goma others may be linked by a bond that forms part of Kaoru aromatic ring system.
[Procedure Amendment 3]
[Document name to be amended] Description [Item name to be amended] 0016
[Correction method] Change [Contents of correction]
[0016]
In another embodiment of the invention, the preferred asymmetric reaction is either hydroformylation or hydrocyanation. More preferably, the reaction is an asymmetric hydroformylation of an olefin and the complex is a rhodium complex. Such asymmetric reactions can cause either enantioselective hydroformylation of prochiral olefins or diastereoselective hydroformylation of enantiomerically enriched chiral olefins. In any case, it is preferred that the required enantioselective excess of the product is at least 60%, preferably at least 80% or more. In such hydroformylation reactions, the olefin is typically, but not always, a prochiral α-olefin (ie, a monosubstituted terminal olefin). Hydroformylation of a prochiral α-olefin (RCH═CH 2 ) results in the formation of two regioisomeric aldehydes: a branched chiral aldehyde (RCH (CHO) CH 3 ) and a linear achiral aldehyde ( RCH 2 CH 2 CHO) can be formed. In the process of the present invention, a branched aldehyde is the main product, so that the branched: linear aldehyde product ratio is at least 3: 1, preferably at least 8: 1 or more. It is desirable that group R in α- olefin, C 1 ~ 30 hydrocarbons (i.e., aryl includes alkyl (cycloalkyl), aralkyl or alkaryl) may be either or heteroatom-based substituent. When R is a hydrocarbon, the hydrocarbon may be unfunctionalized or may be functionalized with one or more non-interfering groups. Without limitation, such non-interfering groups are from the group consisting of alcohols, protected alcohols, protected amines, ketones, nitriles, carboxylic acids, esters, lactones, amides, lactams, carbamates, carbonates and halides. Can be selected. When R is a heteroatom- based substituent, such substituents can be selected from the group consisting of, but not limited to, O-acyl, N-acyl and S-acyl. In a specific embodiment of the invention, the α-olefin is selected from the group consisting of styrene, vinyl acetate and allyl cyanide.
Claims (34)
を含むエナンチオマー濃縮されたキラルなビス（ホスホラン）配位子の遷移金属錯体の存在下で行われる、ヒドロホルミル化、ヒドロシアン化、ヒドロカルボキシル化およびヒドロエステル化からなる群より選択される不斉反応にオレフィンを供するためのプロセス。 As a catalyst, a partial structure according to the following formula (1):
An asymmetric reaction selected from the group consisting of hydroformylation, hydrocyanation, hydrocarboxylation and hydroesterification, carried out in the presence of a transition metal complex of an enantiomerically enriched chiral bis (phosphorane) ligand containing Process for providing olefins.
（ただし、（５）におけるＸはＯまたはＮ−アルキルのいずれかであり、（８）におけるＲはＨまたはアルキルのいずれかである）
によって表される群から選択される、請求項１８に記載のプロセス。 The ligand is represented by the following formulas (3) to (8):
(However, X in (5) is either O or N-alkyl, and R in (8) is either H or alkyl)
The process of claim 18 , selected from the group represented by:
によって表されるようなＰｈ−ＢＰＥである、請求項２４に記載のプロセス。 The ligand is represented by the following formula (9):
25. The process of claim 24 , wherein the process is Ph-BPE as represented by
である、請求項２４に記載のプロセス。 The ligand is bisphopholane according to the following formula (10):
25. The process of claim 24 , wherein
である、請求項２４に記載のプロセス。 The ligand is bisphopholane according to the following formula (11):
25. The process of claim 24 , wherein
である、請求項２４に記載のプロセス。 The ligand is bisphopholane according to the following formula (12):
25. The process of claim 24 , wherein
The process according to claim 30 , wherein the operating temperature is in the range of 20C to 140C.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US67405705P | 2005-04-22 | 2005-04-22 | |
| PCT/US2006/015532 WO2006116344A2 (en) | 2005-04-22 | 2006-04-21 | Asymmetric hydroformylation process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2008538585A JP2008538585A (en) | 2008-10-30 |
| JP2008538585A5 true JP2008538585A5 (en) | 2012-09-27 |
Family
ID=37215385
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP2008507990A Pending JP2008538585A (en) | 2005-04-22 | 2006-04-21 | Asymmetric hydroformylation process |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP1874711A2 (en) |
| JP (1) | JP2008538585A (en) |
| CN (1) | CN101443293A (en) |
| WO (1) | WO2006116344A2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP4500289B2 (en) * | 2005-07-25 | 2010-07-14 | 国立大学法人 千葉大学 | 2,3-bis (dialkylphosphino) pyrazine derivative, method for producing the same, and metal complex having the derivative as a ligand |
| JP2009046469A (en) * | 2007-07-26 | 2009-03-05 | Chiba Univ | Method for preparing optically active allyl compound |
| DE102010043558A1 (en) * | 2010-11-08 | 2012-05-10 | Evonik Oxeno Gmbh | Process for the hydroformylation of unsaturated compounds |
Family Cites Families (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5008457A (en) * | 1990-05-17 | 1991-04-16 | E. I. Du Pont De Nemours And Company | Chiral phospholane transition metal catalysts |
| ZA965990B (en) * | 1995-07-17 | 1997-02-24 | Shell Int Research | Process for the continuous carbonylation of olefins. |
| US6545183B1 (en) * | 1997-11-07 | 2003-04-08 | Chirotech Technology Limited | Process for preparing cyclic phosphines |
| CA2309668A1 (en) * | 1997-12-17 | 1999-06-24 | Chirotech Technology Limited | Asymmetric hydrogenation |
| WO1999059721A1 (en) * | 1998-05-18 | 1999-11-25 | The Penn State Research Foundation | Catalytic asymmetric hydrogenation, hydroformylation, and hydrovinylation via transition metal catalysts with phosphines and phosphites |
| WO2000011008A1 (en) * | 1998-08-21 | 2000-03-02 | The Penn State Research Foundation | Asymmetric catalysis based on chiral phospholanes |
| FR2835833B1 (en) * | 2002-02-13 | 2004-03-19 | Rhodia Polyamide Intermediates | PROCESS FOR THE MANUFACTURE OF NITRILE COMPOUNDS FROM ETHYLENICALLY UNSATURATED COMPOUNDS |
| EP1490379B1 (en) * | 2002-04-04 | 2010-05-19 | Evonik Degussa GmbH | Bisphosphines as bidentate ligands |
-
2006
- 2006-04-21 CN CNA2006800132076A patent/CN101443293A/en active Pending
- 2006-04-21 EP EP06751294A patent/EP1874711A2/en not_active Withdrawn
- 2006-04-21 JP JP2008507990A patent/JP2008538585A/en active Pending
- 2006-04-21 WO PCT/US2006/015532 patent/WO2006116344A2/en active Application Filing
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