JP2010208993A - 2,2’−ビス(ジアルキルホスフィノ)ビフェニル化合物及びその製造方法並びに該化合物を配位子とする金属錯体 - Google Patents
2,2’−ビス(ジアルキルホスフィノ)ビフェニル化合物及びその製造方法並びに該化合物を配位子とする金属錯体 Download PDFInfo
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- JP2010208993A JP2010208993A JP2009056990A JP2009056990A JP2010208993A JP 2010208993 A JP2010208993 A JP 2010208993A JP 2009056990 A JP2009056990 A JP 2009056990A JP 2009056990 A JP2009056990 A JP 2009056990A JP 2010208993 A JP2010208993 A JP 2010208993A
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- Prior art keywords
- bis
- general formula
- dialkylphosphino
- compound
- biphenyl compound
- Prior art date
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- -1 biphenyl compound Chemical class 0.000 title claims abstract description 86
- ZUOUZKKEUPVFJK-UHFFFAOYSA-N phenylbenzene Natural products C1=CC=CC=C1C1=CC=CC=C1 ZUOUZKKEUPVFJK-UHFFFAOYSA-N 0.000 title claims abstract description 67
- 239000004305 biphenyl Substances 0.000 title claims abstract description 60
- 235000010290 biphenyl Nutrition 0.000 title claims abstract description 60
- 239000003446 ligand Substances 0.000 title claims abstract description 28
- 150000004696 coordination complex Chemical class 0.000 title claims abstract description 24
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 17
- 150000001875 compounds Chemical class 0.000 title abstract description 11
- 238000006243 chemical reaction Methods 0.000 claims abstract description 36
- 238000011914 asymmetric synthesis Methods 0.000 claims abstract description 19
- 239000003054 catalyst Substances 0.000 claims abstract description 19
- FFDLFWMUMGTWIB-UHFFFAOYSA-N boron;phosphane Chemical compound [B].P.P FFDLFWMUMGTWIB-UHFFFAOYSA-N 0.000 claims abstract description 9
- 238000005859 coupling reaction Methods 0.000 claims abstract description 8
- 125000001424 substituent group Chemical group 0.000 claims description 17
- 125000004432 carbon atom Chemical group C* 0.000 claims description 14
- 125000000547 substituted alkyl group Chemical group 0.000 claims description 9
- 238000000034 method Methods 0.000 claims description 8
- 125000005843 halogen group Chemical group 0.000 claims description 6
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 claims description 4
- 125000000999 tert-butyl group Chemical group [H]C([H])([H])C(*)(C([H])([H])[H])C([H])([H])[H] 0.000 claims description 4
- XYFCBTPGUUZFHI-UHFFFAOYSA-N Phosphine Natural products P XYFCBTPGUUZFHI-UHFFFAOYSA-N 0.000 abstract description 14
- 239000002246 antineoplastic agent Substances 0.000 abstract description 9
- 206010028980 Neoplasm Diseases 0.000 abstract description 8
- 150000003624 transition metals Chemical group 0.000 abstract description 8
- 229910000073 phosphorus hydride Inorganic materials 0.000 abstract description 7
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 abstract description 4
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- 230000000694 effects Effects 0.000 abstract description 3
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- 206010027476 Metastases Diseases 0.000 abstract description 2
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- 239000010949 copper Substances 0.000 abstract description 2
- 230000009401 metastasis Effects 0.000 abstract description 2
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- 239000004332 silver Substances 0.000 abstract description 2
- 230000002401 inhibitory effect Effects 0.000 abstract 1
- 125000000217 alkyl group Chemical group 0.000 description 29
- 229910052717 sulfur Inorganic materials 0.000 description 22
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 18
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- 125000004437 phosphorous atom Chemical group 0.000 description 10
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- 239000010948 rhodium Substances 0.000 description 10
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- 238000004458 analytical method Methods 0.000 description 7
- 238000003756 stirring Methods 0.000 description 7
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- 201000011510 cancer Diseases 0.000 description 6
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- YLARAMMPZMUNDX-UHFFFAOYSA-N tert-butyl-methyl-(2-phenylphenyl)phosphane Chemical group CC(C)(C)P(C)C1=CC=CC=C1C1=CC=CC=C1 YLARAMMPZMUNDX-UHFFFAOYSA-N 0.000 description 6
- 229910052723 transition metal Inorganic materials 0.000 description 6
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 5
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- 238000001035 drying Methods 0.000 description 4
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- 229910052703 rhodium Inorganic materials 0.000 description 4
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- 238000006467 substitution reaction Methods 0.000 description 4
- 239000005749 Copper compound Substances 0.000 description 3
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
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- LVPKDSXBTYENKG-UHFFFAOYSA-N CC(C)(C)CC(C)(C)P(C)C(C=CC=C1)=C1C1=CC=CC=C1 Chemical group CC(C)(C)CC(C)(C)P(C)C(C=CC=C1)=C1C1=CC=CC=C1 LVPKDSXBTYENKG-UHFFFAOYSA-N 0.000 description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 2
- 206010009944 Colon cancer Diseases 0.000 description 2
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 description 2
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 2
- 125000005073 adamantyl group Chemical group C12(CC3CC(CC(C1)C3)C2)* 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 238000000668 atmospheric pressure chemical ionisation mass spectrometry Methods 0.000 description 2
- 125000002619 bicyclic group Chemical group 0.000 description 2
- MUALRAIOVNYAIW-UHFFFAOYSA-N binap Chemical compound C1=CC=CC=C1P(C=1C(=C2C=CC=CC2=CC=1)C=1C2=CC=CC=C2C=CC=1P(C=1C=CC=CC=1)C=1C=CC=CC=1)C1=CC=CC=C1 MUALRAIOVNYAIW-UHFFFAOYSA-N 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 2
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- JRZJOMJEPLMPRA-UHFFFAOYSA-N olefin Natural products CCCCCCCC=C JRZJOMJEPLMPRA-UHFFFAOYSA-N 0.000 description 1
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F15/00—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table
- C07F15/0006—Compounds containing elements of Groups 8, 9, 10 or 18 of the Periodic Table compounds of the platinum group
- C07F15/0073—Rhodium compounds
- C07F15/008—Rhodium compounds without a metal-carbon linkage
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
- B01J31/24—Phosphines, i.e. phosphorus bonded to only carbon atoms, or to both carbon and hydrogen atoms, including e.g. sp2-hybridised phosphorus compounds such as phosphabenzene, phosphole or anionic phospholide ligands
- B01J31/2404—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring
- B01J31/2409—Cyclic ligands, including e.g. non-condensed polycyclic ligands, the phosphine-P atom being a ring member or a substituent on the ring with more than one complexing phosphine-P atom
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F9/00—Compounds containing elements of Groups 5 or 15 of the Periodic Table
- C07F9/02—Phosphorus compounds
- C07F9/28—Phosphorus compounds with one or more P—C bonds
- C07F9/50—Organo-phosphines
- C07F9/5027—Polyphosphines
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2231/00—Catalytic reactions performed with catalysts classified in B01J31/00
- B01J2231/60—Reduction reactions, e.g. hydrogenation
- B01J2231/64—Reductions in general of organic substrates, e.g. hydride reductions or hydrogenations
- B01J2231/641—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes
- B01J2231/645—Hydrogenation of organic substrates, i.e. H2 or H-transfer hydrogenations, e.g. Fischer-Tropsch processes of C=C or C-C triple bonds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2531/00—Additional information regarding catalytic systems classified in B01J31/00
- B01J2531/80—Complexes comprising metals of Group VIII as the central metal
- B01J2531/82—Metals of the platinum group
- B01J2531/822—Rhodium
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Abstract
【解決手段】2,2’−ビス(ジアルキルホスフィノ)ビフェニル化合物は、ジアルキル(2−ハロゲノフェニル)ホスフィン−ボラン化合物をカップリング反応に付して、ジホスフィン−ボラン中間体を得た後、該中間体を脱ボラン化反応に付すことにより得ることができる。さらに、このビフェニル化合物を配位子とする金属錯体は、不斉合成反応の触媒として用いた場合に高いエナンチオ選択性及び反応活性を示し、各種不斉合成反応に幅広く適用することができる。ビフェニル化合物を配位子とし、金、銀及び銅からなる群から選ばれる遷移金属原子(好ましくは金)と共に形成された金属錯体は、抗癌剤にも有用である。また、癌転移を抑制するためにも使用されることができる。
【選択図】なし
Description
(R,R)−2,2’−ビス(t−ブチルメチルホスフィノ)ビフェニル、(S,S)−2,2’−ビス(t−ブチルメチルホスフィノ)ビフェニル、(R,R)−2,2’−ビス(アダマンチルメチルホスフィノ)ビフェニル、(S,S)−2,2’−ビス(アダマンチルメチルホスフィノ)ビフェニル、(R,R)−2,2’−ビス(1,1,3,3−テトラメチルブチルメチルホスフィノ)ビフェニル、(S,S)−2,2’−ビス(1,1,3,3−テトラメチルブチルメチルホスフィノ)ビフェニル
臭化銅等を用いることができる。銅化合物は一般式(2)で表されるホスフィン−ボラン化合物1モルに対して通常1〜3モルの範囲で用いられる。カップリング反応は、例えば、ジエチルエーテル、テトラヒドロフラン等の有機溶媒中、sec−ブチルリチウム、n−ブチルリチウム等の塩基の存在下で行われる。反応時間は1〜50時間とすることができる。反応温度は−100〜100℃とすることができる。
[Rh((S,S)−(1))(cod)]BF4、[Rh((R,R)−(1))(cod)]BF4、[Rh((S,S)−(1))(nbd)]BF4、[Rh((R,R)−(1))(nbd)]BF4、[Rh((S,S)−(1))(cod)]PF6、
[Rh((R,R)−(1))(cod)]PF6
下記反応式に従い以下の手順で(R)−2−(ボラナト(t−ブチル)メチルホスフィノ)ブロモベンゼンを合成した。
融点 90〜92℃
[α]25 D -28.7 (c 0.515, CHCl3)
1H NMR (500 MHz, CDCl3) δ: 0.20-1.05 (m, 3H), 1.19 (d, J=14.3 Hz, 9H), 1.91 (d, 9.7 Hz, 3H), 7.32 (t, 8.7 Hz, 1H), 7.40 (t, 7.5 Hz, 1H), 7.64 (d, 9.0 Hz, 1H), 8.06 (dd, 12.6,12.9 Hz, 1H)
31P NMR (202 MHz, CDCl3) δ:38.3
APCI-MS:m/z 275, 273 (M++H)
下記反応式に従い以下の手順で(R,R)−2,2’−ビス(t−ブチルメチルホスフィノ)ビフェニルを合成した。
融点 152〜153℃
1H NMR(500 MHz, CDCl3) δ:-0.70-0.40 (m, 6H), 1.07 (d, J=13.2 Hz, 18H), 1.67 (d, 8.9 Hz, 6H), 7.22-7.24 (m, 2H), 7.39-7.47 (m, 4H), 7.54-7.56 (m, 2H)
31P NMR (202 MHz, CDCl3) δ:25.0
APCI-MS:m/z 386 (M+)
融点 106〜108℃
1H NMR(500 MHz, CDCl3) δ: 0.74 (m, 18H), 1.25 (s, 6H), 7.15 (m, 2H), 7.34 (m, 4H), 7.50 (m, 2H)
31P NMR (202 MHz, CDCl3) δ:-23.9
下記反応式に従い以下の手順で(S,S)−(2,2’−ビス(t−ブチルメチルホスフィノ)ビフェニル)(1,5−シクロオクタンジエン)ロジウム(I)テトラフルオロボレートを合成した。
1H NMR (500MHz, CDCl3) δ:0.84 (d, J=14.6 Hz, 18H), 1.65 (d, 6.0 Hz, 6H), 2.22-2.26 (m, 4H), 2.46-2.51 (m, 4H), 4.73-4.74 (m, 2H), 5.40-5.42 (m, 4H), 7.18-7.20 (m, 2H), 7.46-7.47 (m, 2H), 7.52-7.59 (m, 4H)
31P NMR (202 MHz, CDCl3) δ:17.20 (d, 141 Hz)
下記反応式に従い、実施例2で得られた(S,S)−(2,2’−ビス(t−ブチルメチルホスフィノ)ビフェニル)(1,5−シクロオクタンジエン)ロジウム(I)テトラフルオロボレートを不斉水添触媒として用い、以下の手順でデヒドロアミノ酸の不斉還元反応を行った。
Daicel Chiralcel OJ,1.0ml/min,ヘキサン:2−プロパノール=9:1
各エナンチオマーの保持時間:(R体)t1=13.3min,(S体)t2=19.3min
Claims (7)
- R1がt−ブチル基であり、R2がメチル基である請求項2記載の2,2’−ビス(ジアルキルホスフィノ)ビフェニル化合物。
- 請求項1記載の2,2’−ビス(ジアルキルホスフィノ)ビフェニル化合物を配位子とすることを特徴とする金属錯体。
- 前記2,2’−ビス(ジアルキルホスフィノ)ビフェニル化合物が請求項2記載の2,2’−ビス(ジアルキルホスフィノ)ビフェニル化合物であり、不斉合成触媒として用いられる請求項6記載の金属錯体。
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WO2012005200A1 (ja) * | 2010-07-08 | 2012-01-12 | 日本化学工業株式会社 | 光学活性な1,2-ビス(ジアルキルホスフィノ)ベンゼン誘導体の製造方法 |
WO2016093175A1 (ja) * | 2014-12-12 | 2016-06-16 | 国立大学法人名古屋大学 | トリ(ヘテロ)アリールアセトニトリル化合物の製造方法 |
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JP6835801B2 (ja) * | 2018-05-29 | 2021-02-24 | 日本化学工業株式会社 | ホスフィノベンゼンボラン誘導体の製造方法、1,2−ビス(ジアルキルホスフィノ)ベンゼン誘導体の製造方法及び遷移金属錯体 |
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