JP6721891B2 - 1,3−ジアミン誘導体 - Google Patents
1,3−ジアミン誘導体 Download PDFInfo
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- JP6721891B2 JP6721891B2 JP2016102024A JP2016102024A JP6721891B2 JP 6721891 B2 JP6721891 B2 JP 6721891B2 JP 2016102024 A JP2016102024 A JP 2016102024A JP 2016102024 A JP2016102024 A JP 2016102024A JP 6721891 B2 JP6721891 B2 JP 6721891B2
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Description
また、抗菌作用を有する8−オキサ−6−アザビシクロ[3,2,1]オクタン誘導体の例が下記非特許文献2に記載されている。1,3−ジアミンの直接的な不斉合成法として、プロリン触媒を用いたアルデヒドとN−Boc−imineの不斉ダブルマンニッヒ反応が非特許文献1に記載されている。また、非特許文献2にはジエンとアミナ−ルの反応による合成法、非特許文献3にはアルデヒドとアミンならびにエナミンを用いる反応が記載されている。
本実施形態に係る光学活性な1,3−ジアミン誘導体の製造方法は、下記化学式(1)で示される配位子を金属塩に配位させて得られる触媒の存在下で、イミンとマロノニトリルを反応させる。
を反応させることで上記(1)に示される配位子を得ることができる。
本実施例では、下記式(1)で示される配位子を0.005 mmol用い、これに塩化メチレン(4.0 ml)中で塩化ニッケル酢酸パラジウム(II)0.01 mmolを配位させることで触媒としてマロノニトリルのダブルマンニッヒ不斉付加反応を行った。
1H NMR(400MHz,CDCl3):δ7.42(s,10H), 5.54(br,2H),5.29(br,2H), 1.44(s,18H); 13C NMR(100MHz,CDCl3):δ154.1, 134.9, 129.7, 129.1, 127.7, 113.1, 81.4, 56.5, 51.6, 28.2; IR(neat) 1698, 1558, 1540, 1508, 1364, 1161 cm−1;[α]D 18.7= +19.6° (c=1.0, CHCl3, 99%ee). Enantiomeric excess was determined by HPLC with a Chiralpak IA column (hexane:2−propanol = 90:10, 0.5 mL/min, 254 nm) ; major enantiomer tr = 16.8 min, minor enantiomer tr = 19.7 min, 99% ee; HRMS (ESI+) calcd for C27H32N4O4 (M+H) 476.2424 : found 499.2305.
本実施例は、上記実施例1と同一条件で行った。この結果、下記化合物(2−2)を56.6mg得ることが出来た。また、(2−2)の収率は99%(dl/meso =99/1、87% ee)であった。
1H NMR (400MHz,CDCl3):δ8.24 (d,J=8.15Hz,2H), 7.85−7.77(m,4H), 7.65−7.61(m,2H), 6.85(br,2H), 5.84(br, 2H), 1.47(s, 18H) 13C NMR (100MHz,CDCl3):δ153.9, 147.8, 134.6, 131.6, 130.6, 128.7, 126.0, 111.6, 82.0, 50.8, ,50.4, 28.1; IR (neat) 1717, 1532, 1350, 1248,1159, 759 cm−1; [α]D 20.2= −31.6° (c=1.0,CHCl3,87% ee). Enantiomeric excess was determined by HPLC with a Chiralpak IA column (hexane:2−propanol = 70:30, 1.0 mL/min, 254 nm) ; major enantiomer tr = 11.7 min, minor enantiomer tr = 23.3 min, 87% ee; HRMS (ESI+) calcd for C27H30O8N6 (M+H) 567.2198 : found 567.2199.
本実施例は、上記実施例1と同一条件で行った。この結果、下記化合物(2−3)を44.2mg得ることが出来た。また、(2−3)の収率は70%(dl/meso = 80/20、96% ee)であった。
1H NMR (400MHz,CDCl3): δ7.68−7.64(m,4H), 7.46(m,2H), 7.31−7.27(m,2H), 6.18(br,2H), 5.53(d,J=7.85Hz,2H), 1.46(s,18H); 13C NMR(100MHz,CDCl3):δ 135.8, 135.3, 133.6, 131.0, 128.5, 127.6, 124.9, 111.7, 81.6, 54.7, 51.0 28.2; IR (neat) 1717, 1508, 1473, 1368, 1246, 1163, 752 cm−1; [α]D 20.2= +43.5 (c=1.0, CHCl3,96% ee). Enantiomeric excess was determined by HPLC with a Chiralpak AD−H column (hexane:2−propanol = 80:20, 1.0 mL/min, 254 nm) ; major enantiomer tr =6.5 min, minor enantiomer tr = 15 min, 96% ee; HRMS (ESI+) calcd for C27H30O4N4Br2 (M+H) 633.0707 : found 633.0711.
Claims (1)
- 下記式(2)で示される1,3−ジアミン誘導体。
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