JP7186429B2 - キラルボラート塩及びその製造方法 - Google Patents
キラルボラート塩及びその製造方法 Download PDFInfo
- Publication number
- JP7186429B2 JP7186429B2 JP2018221395A JP2018221395A JP7186429B2 JP 7186429 B2 JP7186429 B2 JP 7186429B2 JP 2018221395 A JP2018221395 A JP 2018221395A JP 2018221395 A JP2018221395 A JP 2018221395A JP 7186429 B2 JP7186429 B2 JP 7186429B2
- Authority
- JP
- Japan
- Prior art keywords
- group
- chiral
- substituted
- general formula
- same
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Landscapes
- Pyrane Compounds (AREA)
- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
Description
で表されるキラルボラート塩。
で表される、項1に記載のキラルボラート塩。
で表される化合物。
で表される化合物。
本発明のキラルボラート塩は、一般式(1):
で表されるキラルボラート塩である。
で表されるキラルボラート塩とすることができる。
等が挙げられ、本発明のキラルボレート塩を高い反応性を備えたカチオン種とより安定なイオン対を形成できるキラル非配位性アニオンとするとともに触媒反応におけるエナンチオ選択率により優れる観点からは、
本発明のキラルボラート塩を用いた触媒反応の一例として、本発明のビニルエーテル化合物の環化方法は、本発明のキラルボラート塩(特に、カウンターイオンとして酸性カチオンを有するキラルボラート塩)又は触媒の存在下に、ビニルエーテル化合物を反応させることができる。例えば、一般式(4):
で表される化合物を本発明のキラルボラート塩(特に、カウンターイオンとして酸性カチオンを有するキラルボラート塩)又は触媒の存在下に反応させ、一般式(5A)及び(5B):
で表される化合物を得ることができ、特に、本発明のキラルボラート塩は一般式(5A)で表される化合物を選択的に得ることができる。
本発明のキラルボラート塩の製造方法は特に制限されないが、例えば、以下の反応式1:
に沿って合成することができる。
本工程では、一般式(6)で表される化合物と、一般式(7)で表される化合物とを、塩基の存在下で反応させることで、一般式(3)で表される化合物を得る。
本工程では、一般式(3)で表される化合物と有機金属化合物(有機リチウム化合物、グリニャール試薬等)とを反応させることで、一般式(2)で表される化合物を得る。
本工程では、一般式(2)で表される化合物と、トリアルコキシボラン化合物とを、塩基の存在下で反応させることで、一般式(1)で表されるキラルボラート塩を得る。
合成例1-1:ジエチル(R)-N,N’-[ビナフタレン]-ビス(オキサメート)の合成
合成例2-1:(R)-N,N’-[ビナフタレン]-ビス(ベンジルアミド)の合成
適切な有機金属化合物を用いたこと以外は合成例2-1と同様に、以下の目的化合物を得た。
実施例1-1:テトラデンテートトリエチルアンモニウムボラート1a・HNEt 3 の合成
1a・HNEt3: 1H NMR (500 MHz, CDCl3) δ 8.94 (1H, br), 7.95 (2H, d, J = 7.7 Hz), 7.93 (4H, d, J = 7.7 Hz), 7.87 (2H, d, J = 7.7 Hz), 7.49 (2H, d, J = 7.7 Hz), 7.42 (2H, t, J = 7.7 Hz), 7.33 (4H, t, J = 7.7 Hz), 7.25 (2H, t, J = 7.7 Hz), 7.23 (2H, d, J = 7.7 Hz), 7.13 (2H, t, J = 7.7 Hz), 6.79 (2H, t, J = 7.7 Hz), 6.54 (4H, t, J = 7.7 Hz), 6.30 (4H, d, J = 7.7 Hz), 2.12 (6H, q, J = 7.3 Hz), 0.48 (9H, t, J = 7.3 Hz); 13C NMR (126 MHz, CDCl3) δ 177.9, 146.0, 143.3, 138.4, 133.5, 132.5, 130.6, 129.1, 128.4, 127.8, 127.6, 127.54, 127.51, 127.4, 127.3, 126.9, 126.3, 125.7, 125.2, 85.5, 46.1, 8.3; 11B NMR (160 MHz, CDCl3) δ 11.3; IR (film): 3060, 2728, 1641, 1592, 1506, 1472, 1390, 1136, 1117, 1081, 1045, 1023, 910, 809 cm-1; HRMS (ESI) Calcd for C48H32N2O4B- ([M-H NEt3]-) 711.2450. Found 711.2436.; [α]D 27 -264.8 (c = 11.3, CHCl3)。
適切な基質を用いたこと以外は実施例1-1と同様に、以下の目的化合物を得た。
1c・HNEt3 (Ar = 3-MeC6H4): 1H NMR (500 MHz, CDCl3) δ 9.02 (1H, br), 7.93 (2H, d, J = 7.8 Hz), 7.91 (2H, d, J = 7.8 Hz), 7.87 (2H, s), 7.72 (2H, d, J = 7.8 Hz), 7.61 (2H, dd, J = 7.8, 3.0 Hz), 7.40 (2H, t, J = 7.8 Hz), 7.22 (2H, t, J = 7.8 Hz), 7.19 (2H, d, J = 7.8 Hz), 7.14-7.06 (4H, m), 6.61 (2H, d, J = 7.8 Hz), 6.49 (2H, t, J = 7.8 Hz), 6.16 (2H, d, J = 7.8 Hz), 6.15 (2H, s), 2.40 (6H, s), 2.17-2.05 (6H, m), 1.61 (6H, s), 0.57-0.47 (9H, m); 13C NMR (126 MHz, CDCl3) δ 178.1, 146.1, 143.2, 138.4, 136.93, 136.85, 133.6, 132.5, 130.3, 129.1, 128.5, 128.4, 128.1, 127.9, 127.61, 127.57, 127.3, 127.2, 127.1, 125.6, 125.1, 125.0, 124.8, 85.5, 45.9, 22.0, 21.0, 8.2; 11B NMR (160 MHz, CDCl3) δ 10.8; IR (film): 3022, 2711, 1641, 1506, 1472, 1391, 1136, 1121, 1055, 1025, 906, 820 cm-1; HRMS (ESI) Calcd for C52H40N2O4B-([M-H NEt3]-) 767.3076. Found 767.3091.; [α]D 26 -312.1 (c = 10.3, CHCl3).
1d・HNEt3 (Ar =3,5-Me2C6H3): 1H NMR (500 MHz, CDCl3) δ 9.29 (1H, brs), 7.89 (2H, d, J = 7.7 Hz), 7.88 (2H, d, J = 7.7 Hz), 7.60 (2H, d, J = 7.7 Hz), 7.59 (4H, s), 7.37 (2H, t, J = 7.7 Hz), 7.17 (2H, d, J = 7.7 Hz), 7.10 (2H, t, J = 7.7 Hz), 6.89 (2H, s), 6.44 (2H, s), 6.02 (4H, s), 2.34 (12H, s), 2.15 (6H, br), 1.64 (12H, s), 0.62-0.53 (9H, m); 13C NMR (126 MHz, CDCl3) δ 178.3, 146.1, 143.5, 138.5, 136.5, 136.4, 133.6, 132.5, 130.3, 129.0, 128.5, 128.4, 128.2, 128.1, 127.8, 125.6, 125.5, 125.4, 125.0, 85.7, 45.9, 21.9, 21.0, 8.2; 11B NMR (160 MHz, CDCl3) δ 11.0; IR (film): 3005, 2912, 1639, 1592, 1506, 1470, 1392, 1203, 1120, 1048, 1026, 909, 853 cm-1; HRMS (ESI) Calcd for C56H48N2O4B-([M-H NEt3]-) 823.3702. Found 823.3711.; [α]D 27 -271.3 (c = 12.0, CHCl3).
1e・HNEt3 (Ar =3,5-nBu2C6H3): 1H NMR (500 MHz, CDCl3) δ 9.58 (1H, br), 7.86 (2H, d, J = 7.6 Hz), 7.82 (2H, d, J = 7.6 Hz), 7.58 (4H, s), 7.57 (2H, d, J = 7.6 Hz), 7.36 (2H, t, J = 7.6 Hz), 7.13 (2H, d, J = 7.6 Hz), 7.07 (2H, t, J = 7.6 Hz), 6.88 (2H, s), 6.46 (2H, s), 6.13 (4H, s), 2.61 (8H, t, J = 7.3 Hz), 2.24-2.11 (6H, m), 1.95 (4H, ddd, J = 14.8, 9.3, 5.3 Hz), 1.85 (4H, ddd, J = 14.8, 9.3, 5.3 Hz), 1.59 (8H, quin, J = 7.3 Hz), 1.33 (8H, sex, J = 7.3 Hz), 1.24-1.08 (16H, m), 0.87 (12H, t, J = 7.3 Hz), 0.80 (12H, t, J = 7.3 Hz), 0.63-0.56 (9H, m); 13C NMR (126 MHz, CDCl3) δ 178.4, 145.9, 143.7, 141.4, 141.3, 138.7, 133.6, 132.4, 130.4, 128.8, 128.4, 128.0, 127.9, 126.7, 126.2, 125.5, 125.3, 125.2, 124.9, 85.7, 45.8, 36.1, 35.5, 34.0, 33.6, 22.7, 22.6, 14.2, 14.1, 8.2; 11B NMR (160 MHz, CDCl3) δ 11.0; IR (film): 2929, 2886, 1640, 1593, 1505, 1466, 1393, 1230, 1103, 1072, 1026, 819 cm-1; HRMS (ESI) Calcd for C80H96N2O4B- ([M-H NEt3]-) 1159.7458. Found 1159.7446.; [α]D 26 -188.7 (c = 11.9, CHCl3)。
実施例2-1:テトラデンテートキラルハイドロジェンボラート1a・Hの合成
1a・H: 1H NMR (500 MHz, DMSO-d6) δ 8.03 (2H, d, J = 7.8 Hz), 7.96 (2H, d, J = 7.8 Hz), 7.84 (4H, d, J = 7.8 Hz), 7.44 (2H, t, J = 7.8 Hz), 7.38 (4H, t, J = 7.8 Hz), 7.29 (4H, t, J = 7.8 Hz), 7.21 (2H, t, J = 7.8 Hz), 7.00 (2H, d, J = 7.8 Hz), 6.82 (2H, t, J = 7.8 Hz), 6.55 (4H, t, J = 7.8 Hz), 6.30 (4H, d, J = 7.8 Hz), one proton was not found due to broadening.; 13C NMR (126 MHz, DMSO-d6) δ 175.6, 146.0, 144.4, 138.7, 132.9, 131.7, 130.0, 128.2, 128.0, 127.6, 127.1, 127.0, 126.9, 126.7, 126.5, 126.4, 125.7, 125.5, 124.7, 84.1; 11B NMR (160 MHz, DMSO-d6) δ 10.5; IR (film): 3340, 3059, 1714, 1658, 1592, 1489, 1395, 1264, 1187, 1023, 1003, 909, 814 cm-1; HRMS (ESI) Calcd for C48H32N2O4B-([M-H]-) 711.2450. Found 711.2468.; [α]D 28 -179.9 (c = 10.7, CH2Cl2)。
適切な基質を用いたこと以外は実施例2-1と同様に、以下の目的化合物を得た。
1c・H (Ar = 3-MeC6H4): 1H NMR (500 MHz, DMSO-d6) δ 8.00 (2H, d, J = 7.9 Hz), 7.99 (2H, d, J = 7.9 Hz), 7.73 (2H, s), 7.62 (2H, d, J = 7.9 Hz), 7.42 (2H, t, J = 7.9 Hz), 7.36 (2H, d, J = 7.9 Hz), 7.24 (2H, t, J = 7.9 Hz), 7.18 (2H, t, J = 7.9 Hz), 7.10 (2H, d, J = 7.9 Hz), 6.95 (2H, d, J = 7.9 Hz), 6.61 (2H, d, J = 7.9 Hz), 6.53 (2H, t, J = 7.9 Hz), 6.15 (2H, d, J = 7.9 Hz), 6.11 (2H, s), 2.38 (6H, s), 1.60 (6H, s), one proton was not found due to broadening.; 13C NMR (126 MHz, DMSO-d6) δ 175.7, 146.1, 144.6, 138.6, 135.9, 135.7, 133.0, 131.7, 129.8, 128.3, 128.2, 127.64, 127.55, 127.5, 127.0, 126.9, 126.8, 126.4, 126.3, 125.4, 124.7, 124.44, 124.39, 84.0, 21.5, 20.5; 11B NMR (160 MHz, DMSO-d6) δ 10.4; IR (film): 3059, 2918, 1647, 1604, 1592, 1474, 1411, 1254, 1125, 1040, 817 cm-1; HRMS (ESI) Calcd for C52H40N2O4B-([M-H]-) 767.3076. Found 767.3107.; [α]D 27 -322.0 (c = 10.2, CH2Cl2).
1d・H (Ar = 3,5-Me2C6H3): 1H NMR (500 MHz, DMSO-d6) δ 7.97 (2H, d, J = 7.9 Hz), 7.96 (2H, d, J = 7.9 Hz), 7.43 (4H, s), 7.39 (2H, t, J = 7.9 Hz), 7.34 (2H, d, J = 7.9 Hz), 7.16 (2H, t, J = 7.9 Hz), 6.93 (2H, d, J = 7.9 Hz), 6.89 (2H, s), 6.41 (2H, s), 5.96 (4H, s), 2.31 (12H, s), 1.64 (12H, s), one proton was not found due to broadening.; 13C NMR (126 MHz, DMSO-d6) δ 175.8, 146.3, 145.0, 138.7, 135.6, 135.3, 133.0, 131.7, 129.8, 128.2, 127.8, 127.7, 127.2, 126.9, 125.3, 125.0, 124.6, 84.3, 21.5, 20.6, two carbon atoms were not found probably due to overlapping.; 11B NMR (160 MHz, DMSO-d6) δ 11.2; IR (film): 2916, 1663, 1594, 1506, 1472, 1405, 1265, 1087, 1037, 852, 815 cm-1; HRMS (ESI) Calcd for C56H48N2O4B-([M-H]-) 823.3702. Found 823.3715.; [α]D 27 -153.3 (c = 10.1, CH2Cl2).
1e・H (Ar = 3,5-nBu2C6H3): 1H NMR (500 MHz, DMSO-d6) δ 7.94 (2H, d, J = 8.1 Hz), 7.91 (2H, d, J = 8.1 Hz), 7.49 (4H, s), 7.39 (2H, t, J = 8.1 Hz), 7.29 (2H, d, J = 8.1 Hz), 7.14 (2H, t, J = 8.1 Hz), 6.90 (2H, d, J = 8.1 Hz), 6.89 (2H, s), 6.44 (2H, s), 6.01 (4H, s), 2.58 (8H, t, J = 7.3 Hz), 1.96-1.88 (4H, m), 1.87-1.80 (4H, m), 1.55 (8H, quin, J = 7.3 Hz), 1.29 (8H, sex, J = 7.3 Hz), 1.04-1.14 (16H, m), 0.84 (12H, t, J = 7.3 Hz), 0.77 (12H, t, J = 7.3 Hz), one proton was not found due to broadening.; 13C NMR (126 MHz, DMSO-d6) δ 176.3, 146.1, 144.8, 140.4, 140.2, 138.8, 133.0, 131.6, 129.9, 128.1, 128.0, 127.6, 127.0, 126.1, 125.6, 125.1, 124.94, 124.86, 124.6, 84.4, 35.3, 34.7, 33.5, 33.2, 21.83, 21.79, 13.9, 13.8; 11B NMR (160 MHz, DMSO-d6) δ 10.6; IR (film): 2956, 2929, 1653, 1596, 1507, 1457, 1396, 1149, 1074 cm-1; HRMS (ESI) Calcd for C80H96N2O4B-([M-H]-) 1159.7458. Found 1159.7478.; [α]D 28 -111.0 (c = 10.4, CH2Cl2)。
実施例3-1:(E)-5-ビニルオキシ-3-フェニルペント-2-エンの不斉プリンス型反応
3a: 1H NMR (500 MHz CDCl3) major diastereomer δ 7.40-7.30 (4H, m), 7.28-7.24 (1H, m), 5.96 (1H, t, J = 2.5 Hz), 4.39 (1H, ddd, J = 17.0, 2.9, 2.5 Hz), 4.35 (1H, ddd, J = 17.0, 2.9, 2.5 Hz), 3.83 (1H, qd, J = 6.8, 2.9 Hz), 2.60-2.52 (1H, m), 1.28 (3H, d, J = 6.8 Hz), 0.98 (3H, d, J = 6.8 Hz); 13C NMR (126 MHz, CDCl3) δ 141.5, 140.0, 128.6, 127.3, 125.7, 122.2, 72.8, 67.0, 35.2, 18.5, 12.5; IR (film): 2972, 2808, 1496, 1445, 1383, 1142, 1123, 1079, 1017, 865 cm-1; HRMS (ESI) Calcd for C13H17O+([M+H]+) 189.1274. Found 189.1276. HPLC OJ3, H/EtOH = 99: 1, flow rate = 1.0 mL/min, 30℃, λ= 254 nm, 8.8 min (major enantiomer), 9.7 min (minor enantiomer)。
Claims (4)
- 請求項1又は2に記載のキラルボラート塩を含有し、且つ、前記Yが酸性カチオンである、触媒。
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018221395A JP7186429B2 (ja) | 2018-11-27 | 2018-11-27 | キラルボラート塩及びその製造方法 |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2018221395A JP7186429B2 (ja) | 2018-11-27 | 2018-11-27 | キラルボラート塩及びその製造方法 |
Publications (2)
Publication Number | Publication Date |
---|---|
JP2020083826A JP2020083826A (ja) | 2020-06-04 |
JP7186429B2 true JP7186429B2 (ja) | 2022-12-09 |
Family
ID=70906446
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
JP2018221395A Active JP7186429B2 (ja) | 2018-11-27 | 2018-11-27 | キラルボラート塩及びその製造方法 |
Country Status (1)
Country | Link |
---|---|
JP (1) | JP7186429B2 (ja) |
Family Cites Families (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
AU4645996A (en) * | 1995-12-21 | 1997-07-17 | Northwestern University | High oxidation state metal oxo complexes of the phab ligand |
-
2018
- 2018-11-27 JP JP2018221395A patent/JP7186429B2/ja active Active
Non-Patent Citations (5)
Title |
---|
Albano, Vincenzo Giulio et al.,Synthesis and Crystallographic Characterization of Chiral Bis-oxazoline-amides. Fine-Tunable Ligands for Pd-Catalyzed Asymmetric Alkylations,Journal of Organic Chemistry,2006年,71(17),pp. 6451-6458 |
Clarke, Rebecca et al.,Circularly Polarised Luminescence from Helically Chiral "Confused" N,N,O,C-Boron-Chelated Dipyrromethenes (BODIPYs),ChemPhotoChem,2017年,1(11),pp. 513-517 |
Ferrando-Soria, Jesus et al.,Rational Enantioselective Design of Chiral Heterobimetallic Single-Chain Magnets: Synthesis, Crystal Structures and Magnetic Properties of Oxamato-Bridged MIICuII Chains (M = Mn, Co),Chemistry - A European Journal ,2011年,17(44),pp. 12482-12494 |
Ishihara, Kazuaki et al.,A New Powerful and Practical BLA Catalyst for Highly Enantioselective Diels-Alder Reaction: An Extreme Acceleration of Reaction Rate by Broensted Acid,Journal of the American Chemical Society ,1996年,118(12),pp. 3049-3050 |
Zhou, Yan et al.,Chiral spiroborate esters catalyzed highly enantioselective direct aldol reaction,Tetrahedron,2006年,62(24),pp. 5692-5696 |
Also Published As
Publication number | Publication date |
---|---|
JP2020083826A (ja) | 2020-06-04 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
JP6049804B2 (ja) | 環系芳香族のフッ素化 | |
JP2021098722A (ja) | 金属錯体 | |
Richter-Addo et al. | New strategies for enantioselective syntheses of 1-alkyl-and 1, 4-dialkyl-1, 2, 3, 4-tetrahydroisoquinolines: diastereoselective additions of nucleophiles and electrophiles to isoquinoline mediated by an easily resolved and recycled chiral transition metal auxiliary | |
Yap et al. | Development of a novel chiral palladacycle and its application in asymmetric hydrophosphination reaction | |
JP7186429B2 (ja) | キラルボラート塩及びその製造方法 | |
CN113583042A (zh) | 一种磷酰氟类化合物的制备方法 | |
JP2014527534A (ja) | スピロベンジルアミン−ホスフィン及びその製造方法並びにその使用 | |
CN103748065B (zh) | 2-烯基胺化合物的制造方法 | |
Zhang et al. | Asymmetric synthesis of 1, 2-bis (diphenylphosphino)-1-phenylethane via a chiral palladium template promoted hydrophosphination reaction | |
Alfonso et al. | Optically active tetraazamacrocycles analogous to cyclam | |
CN109666044B (zh) | 基于[2.2]对环芳烷骨架的有机磷化合物及其中间体和制备方法与用途 | |
JP4474861B2 (ja) | 光学活性四級アンモニウム塩、その製造法、並びにそれを用いた光学活性α−アミノ酸誘導体の製造法 | |
CN107880022B (zh) | 一种手性含咪唑吡啶酰胺类的化合物及其制备方法和应用 | |
Palacios et al. | Easy and efficient generation of reactive anions with free and supported ylides as neutral Brønsted bases | |
CN115340572B (zh) | 一种含有氧杂蒽骨架的双膦配体及其合成与应用 | |
JP5569938B2 (ja) | ピロリジン誘導体及びその製造方法 | |
CN114380863B (zh) | 金鸡纳碱衍生的nnp配体及其制备方法与用途 | |
Shimizu et al. | Mechanistic Study of the Palladium-Catalyzed Stereoselective Cross-Coupling Reaction of 1, 1-Dibromo-3, 3, 3-trifluoro-2-tosyloxypropene | |
CN109776546A (zh) | 一种制备吲哚并吡咯酮化合物的方法 | |
WO2006079819A2 (en) | Improved method for the preparation of enantiomerically enriched secondary alcohols by the addition of organoaluminium reagents to carbonyl compounds | |
CN116891501A (zh) | 一种含膦螺旋手性化合物及其制备方法和应用 | |
CN116768733A (zh) | 芳基环状铵盐的芳基化和硅基化方法 | |
Tsuno et al. | Synthesis of chiral-at-metal half-sandwich ruthenium (II) complexes with the CpH (PNMent) tripod ligand | |
Khan | CH Activation Using Boron | |
CN103764613A (zh) | 2-烯基胺化合物的制造方法 |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
A80 | Written request to apply exceptions to lack of novelty of invention |
Free format text: JAPANESE INTERMEDIATE CODE: A80 Effective date: 20181225 |
|
A621 | Written request for application examination |
Free format text: JAPANESE INTERMEDIATE CODE: A621 Effective date: 20211025 |
|
A977 | Report on retrieval |
Free format text: JAPANESE INTERMEDIATE CODE: A971007 Effective date: 20220616 |
|
A131 | Notification of reasons for refusal |
Free format text: JAPANESE INTERMEDIATE CODE: A131 Effective date: 20220705 |
|
A521 | Request for written amendment filed |
Free format text: JAPANESE INTERMEDIATE CODE: A523 Effective date: 20220830 |
|
TRDD | Decision of grant or rejection written | ||
A01 | Written decision to grant a patent or to grant a registration (utility model) |
Free format text: JAPANESE INTERMEDIATE CODE: A01 Effective date: 20221115 |
|
A61 | First payment of annual fees (during grant procedure) |
Free format text: JAPANESE INTERMEDIATE CODE: A61 Effective date: 20221121 |
|
R150 | Certificate of patent or registration of utility model |
Ref document number: 7186429 Country of ref document: JP Free format text: JAPANESE INTERMEDIATE CODE: R150 |