CN113087689B - 5-氨基-γ-内酯衍生物的简便合成方法 - Google Patents

5-氨基-γ-内酯衍生物的简便合成方法 Download PDF

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CN113087689B
CN113087689B CN202110256759.6A CN202110256759A CN113087689B CN 113087689 B CN113087689 B CN 113087689B CN 202110256759 A CN202110256759 A CN 202110256759A CN 113087689 B CN113087689 B CN 113087689B
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CN113087689A (zh
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何炜
张露文
邓晓军
张俊娜
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Air Force Medical University of PLA
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Abstract

本发明公开了结构通式(Ⅰ)所示的5‑氨基‑γ‑内酯类衍生物的合成方法，其以结构式（II）所示的4‑戊烯酸类化合物为底物，采用2,6‑二甲氧基‑1‑碘苯/间氯过氧苯甲酸催化体系，苯磺酰亚胺类化合物为氮源，室温反应构建结构式（I）所示的5‑氨基‑γ‑内酯衍生物。本发明使用绿色芳基碘/氧化剂体系，避免了有毒过渡金属的使用；反应条件温和，可以在空气、室温条件下进行；反应时间短，底物适用范围广；后处理操作简单，产物易纯化。本发明提供一种转化率高、产率高、区域选择性高合成5‑氨基‑γ‑内酯衍生物的新方法。

Description

5-氨基-γ-内酯衍生物的简便合成方法
技术领域
本发明涉及一种5-氨基-γ-内酯衍生物的简便合成方法，属于有机合成技术领域。
背景技术
5-氨基-γ-内酯衍生物是一种具有重要价值的有机分子骨架，不仅存在于许多具有生物活性的天然分子中，并且可作为一类合成中间体来构建更多有用的骨架结构，例如1,2-氨基醇衍生物、四氢呋喃、内酰胺等。关于5-氨基-γ-内酯化合物的合成，通过不饱和羧酸或其衍生物的分子内直接环化/胺化来合成5-氨基-γ-内脂化合物的方法主要为过渡金属催化，其中金属铜催化的氧化胺化反应得到巨大的发展。多种过渡金属铜催化烯烃氧化胺化反应的方法运用于合成具有不同氮取代基团的γ-内脂，包括4-硝基苯磺酰胺、亚胺碘、叠氮三甲基硅烷、邻苯甲酰羟胺、N-氟代双苯磺酰胺、富电子胺NHR1R2。从反应试剂而言：部分氮源（邻苯甲酰羟胺、亚胺碘）需要预先合成，不稳定，且对处理敏感;过渡金属环境不友好，不符合绿色化学理念。从反应条件而言：反应条件苛刻，如高温、不稳定的反应体系、不开放的反应环境（排气、气体保护）也降低了此类方法的适用性。从反应底物而言，铜催化自由基型的氧化胺化反应，烯烃通常需要进行活化，限制底物类型。
近年来，芳基碘/氧化剂体系能原位生成活性催化剂高价碘（Ⅲ）试剂而被广泛的应用于各类有机反应中，可作为过渡金属氧催化烯烃双官能化的绿色替代试剂。因此，各种亲核试剂例如卤素、-OH、-CF3、-SCF3、-OTs、-OAc、磷酸化酰基等）都被有效地运用于碘催化烯烃的官能化反应中，高效地合成内酯化合物。由于氮试剂与芳基碘/氧化剂体系中的氧化剂或羧酸烯烃底物往往不兼容，因而不能原位生成高价碘（Ⅲ）试剂从而无法催化反应循环。因此，关于使用芳基碘/氧化剂体系或高价碘试剂来催化不饱和羧酸烯烃合成5-氨基-γ-内脂衍生物的方法还没有。
发明内容
针对现有方法的不足，本发明提供一种原料易得、工艺简单、反应条件温和、区域选择性高、专向合成5-氨基-γ-内酯衍生物的新方法。
本发明实现过程如下：
一种5-氨基-γ-内酯衍生物的合成方法：以结构式（II）所示的4-戊烯酸类化合物为底物，采用2,6-二甲氧基-1-碘苯/间氯过氧苯甲酸催化体系，苯磺酰亚胺类化合物为氮源，反应得到结构式（I）所示的5-氨基-γ-内酯衍生物，
R1和R2独立地选自氢、C1~C7的烷基、C1~C7的不饱和烷基、C2~C5的烷基羧基、苯基或取代的苯基、苄基或取代的苄基、萘基或取代的萘基，所述取代的苯基、苄基或萘基中的取代基为C1~C5的烷基、C1~C5的烷氧基、卤素、硝基、三氟甲基、C1~C7的酯基、C4~C10的杂环基，所述杂环基为氧杂环、氮杂环、硫杂环；
或R1和R2形成C3~ C6的环烷基或杂环基，或取代的C4~ C15的环烷基或杂环基；
R3选自氢、C1~C7的烷基、苯基、苄基；
或R1、R2和R3形成C4~ C5的环烷基、杂环基、苯并基，或C4~ C15的取代的环烷基、杂环基或苯并基，所述的取代基为C1~C7的烷基、C1~C7的不饱和烷基、卤素、硝基、三氟甲基，C4~C6的环烷基；
R4和R5独立地选自氢、C1~C5的烷基、苯基、苄基；
R6选自苯基或取代的苯基，所述取代的苯基中的取代基为C1~C5的烷基、C1~C5的烷氧基、硝基、三氟甲基、卤素。
所述苯磺酰亚胺类化合物选自4-甲基-N-甲苯磺酰基苯磺酰胺、4-硝基-N-((4-硝基苯基)磺酰基)苯磺酰胺、N-（苯磺酰基）苯磺酰胺。
本发明的优点在于：1）采用2,6-二甲氧基-1-碘苯/间氯过氧苯甲酸催化体系，高区域选择性地合成五元环产物，同时降低了副产物双氧化产物的转化，提高了目标化合物的转化率；2）该方法避免了有毒过渡金属的使用且该催化体系后处理简单，产物易于纯化，对环境无污染；3）反应条件温和，可以在空气、室温条件下进行，反应时间短（7小时之内反应完全），对各种骨架结构的底物都能实现较好转化，产率65 ~ 95%。
具体实施方式
实施例1 化合物I-1的合成
向反应烧瓶中加入2,6-二甲氧基-1-碘苯（催化量），间氯过氧苯甲酸（过量），4-甲基-N-甲苯磺酰基苯磺酰胺（过量），乙腈中溶解。然后再加入2,2-苯基-4-戊烯酸II-1（2mmol）。反应混合物室温条件下继续搅拌2.5小时。通过薄层色谱检测反应过程。反应完成后，加入碱调节pH，乙酸乙酯萃取，低温减压蒸馏去除溶剂。所得残渣经柱层析纯化，得到5-氨基-γ-内酯类化合物I-1（白色固体，收率90%，1.04克）。该产物为新化合物，结构经1HNMR, 13C NMR，HRMS确证。
1(400 MHz, CDCl3) δ 7.92 (d, J = 8.0 Hz, 4H), 7.36 – 7.21 (m, 14H),4.64 – 4.58 (m, 1H), 4.16 (dd, J = 15.6, 6.4 Hz, 1H), 3.88 (dd, J = 15.6, 4.8Hz, 1H), 2.95 (dd, J = 13.2, 5.2 Hz, 1H), 2.69 (dd, J = 12.8, 10.8 Hz, 1H),2.43 (s, 6H);
13C NMR (100 MHz, CDCl3) δ 176.0, 145.4, 141.4, 139.4, 136.3, 129.8,129.0, 128.6, 128.4, 127.8, 127.7, 127.3, 127.2, 75.2, 57.8, 51.2, 41.0,21.7;
HRMS: [M+Na]+ 计算值C31H29NO6S2Na+ 598.1329,实际值598.1335。
实施例2 化合物I-2的合成
向反应烧瓶中加入2,6-二甲氧基-1-碘苯（催化量），间氯过氧苯甲酸（过量），4-硝基-N-((4-硝基苯基)磺酰基)苯磺酰胺（过量），乙腈中溶解。然后再加入2,2-苯基-4-戊烯酸II-1（2 mmol）。反应混合物室温条件下继续搅拌5小时。通过薄层色谱检测反应过程。反应完成后，加入碱调节pH，乙酸乙酯萃取，低温减压蒸馏去除溶剂。所得残渣经柱层析纯化，得到5-氨基-γ-内酯类化合物I-2（白色固体，收率85%，1.08克）。该产物为新化合物，结构经1H NMR, 13C NMR，HRMS确证。
1 (400 MHz, CDCl3) δ 8.38 – 8.24 (m, 8H), 7.39 – 7.17 (m, 10H), 4.63 –4.53 (m, 1H), 4.22 (dd, J = 16.2, 8.0 Hz, 1H), 3.98 – 3.89 (m, 1H), 3.01 (dd,J = 13.2, 5.2 Hz, 1H), 2.61 (dd, J = 13.2, 10.0 Hz, 1H);
13C NMR (100 MHz, CDCl3) δ 175.5, 150.9, 144.0, 140.9, 139.3, 130.3,129.4, 129.1, 128.6, 128.1, 127.7, 127.5, 127.0, 124.4, 75.3, 57.5, 52.5,40.4;
HRMS: [M+H]+ 计算值C29H24N3O10S2 + 638.0898,实际值638.0893。
实施例3 化合物I-3的合成
向反应烧瓶中加入2,6-二甲氧基-1-碘苯（催化量），间氯过氧苯甲酸（过量），N-（苯磺酰基）苯磺酰胺（过量），乙腈中溶解。然后再加入2,2-苯基-4-戊烯酸II-1（2 mmol）。反应混合物室温条件下继续搅拌5小时。通过薄层色谱检测反应过程。反应完成后，加入碱调节pH，乙酸乙酯萃取，低温减压蒸馏去除溶剂。所得残渣经柱层析纯化，得到5-氨基-γ-内酯类化合物I-3（白色固体，收率86%，0.94克）。该产物为新化合物，结构经1H NMR, 13CNMR，HRMS确证。
1 (400 MHz, CDCl3) δ 8.06 (d, J = 7.6 Hz, 4H), 7.64 (t, J = 7.6 Hz,2H), 7.53 (t, J = 7.6 Hz, 4H), 7.39 – 7.21 (m, 10H), 4.63 (dq, J = 10.4, 5.2Hz, 1H), 4.20 (dd, J = 16.0, 6.4 Hz, 1H), 3.90 (dd, J = 16.0, 4.8 Hz, 1H),2.98 (dd, J = 13.2, 5.2 Hz, 1H), 2.70 (dd, J = 13.2, 10.2 Hz, 1H);
13C NMR (100 MHz, CDCl3) δ 176.0, 141.4, 139.4, 139.1, 134.3, 129.2,129.0, 128.6, 128.5, 127.9, 127.7, 127.4, 127.2, 75.2, 57.8, 51.5, 41.0;
HRMS: [M+Na]+ 计算值C29H25NO6S2Na+ 570.1016,实际值570.1011;
实施例4 ~ 22的方法步骤同实施例1，合成得到化合物I-4 ~ I-22，其结构表征数据如下。
1 (400 MHz, CDCl3) δ 7.94 (d, J = 8.0 Hz, 4H), 7.35 (d, J = 8.0 Hz,4H), 4.86 - 4.79 (m, 1H), 4.07 (dd, J = 15.6, 7.6 Hz, 1H), 3.65 (dd, J =15.6, 4.4 Hz, 1H), 2.56 – 2.47 (m, 2H), 2.45 (s, 6H), 2.34 – 2.21 (m, 1H),1.95 (ddd, J = 16.8, 13.2, 8.8 Hz, 1H);
13C NMR (100 MHz, CDCl3) δ 176.0, 145.4, 136.1, 129.7, 128.7, 78.5,51.2, 28.0, 25.2, 21.7;
HRMS: [M+Na]+ 计算值C19H21NO6S2Na+ 446.0703,实际值446.0716。
1(400 MHz, CDCl3) δ 7.95 (d, J = 7.6 Hz, 4H), 7.35 (d, J = 8.0 Hz,4H), 4.72 (dt, J = 10.0, 4.4 Hz, 1H), 4.10 (dd, J = 15.6, 7.2 Hz, 1H), 3.70(dd, J = 16.0, 3.6 Hz, 1H), 2.45 (s, 6H), 2.10 (dd, J = 12.8, 6.0 Hz, 1H),1.80 – 1.74 (m, 1H), 1.23 (s, 3H), 1.20 (s, 3H);
13C NMR (100 MHz, CDCl3) δ 180.6, 145.3, 136.2, 129.7, 128.7, 75.3,51.9, 40.6, 40.1, 24.9, 24.4, 21.7;
HRMS: [M+Na]+ 计算值C21H25NO6S2Na+ 474.1016,实际值474.1016。
1 (400 MHz, CDCl3) δ 7.95 (d, J = 8.0 Hz, 4H), 7.35 (d, J = 8.0 Hz,4H), 4.66 (m, 1H), 4.06 (dd, J = 15.6, 7.2 Hz, 1H), 3.68 (dd, J = 15.6, 4.4Hz, 1H), 2.45 (s, 6H), 2.03 (dd, J = 13.2, 6.8 Hz, 1H), 1.85 (dd, J = 12.8,9.2 Hz, 1H), 1.58 – 1.15 (m, 8H), 0.94 – 0.84 (m, 6H);
13C NMR (100 MHz, CDCl3) δ 179.9, 145.3, 136.2, 129.7, 128.7, 75.3,52.2, 47.8, 39.0, 38.4, 35.7, 21.7, 17.6, 17.6, 14.4, 14.4;
HRMS: [M+Na]+ 计算值C25H33NO6S2Na+ 530.1642,实际值530.1645。
1 (400 MHz, CDCl3) δ 7.92 (d, J = 8.4 Hz, 4H), 7.31 (d, J = 8.0 Hz,4H), 7.13 (dd, J = 18.8, 8.8 Hz, 4H), 6.83 (dd, J = 15.2, 8.8 Hz, 4H), 4.63 –4.56 (m, 1H), 4.14 (dd, J = 16.0, 6.4 Hz, 1H), 3.85 (dd, J = 15.6, 4.8 Hz,1H), 3.79 (d, J = 10.4 Hz, 6H), 2.89 (dd, J = 12.8, 4.8Hz, 1H), 2.61 (dd, J =13.2, 10.4 Hz, 1H), 2.43 (s, 6H);
13C NMR (100 MHz, CDCl3) δ 176.6, 159.0, 158.61, 145.4, 136.2, 133.9,131.4, 129.8, 128.8, 128.6, 128.3, 114.2, 113.7, 75.2, 56.6, 55.3, 55.3,51.2, 41.2, 21.7;
HRMS: [M+Na]+ 计算值C33H33NO6S2Na+ 658.1540,实际值658.1534。
1 (400 MHz, CDCl3) δ 7.73 (d, J = 8.4 Hz, 4H), 7.36 – 7.27 (m, 10H),7.22 – 7.16 (m, 4H), 3.71-3.64 (m, 1H), 3.37 (dd, J = 15.6, 6.8 Hz, 1H), 3.24– 3.09 (m, 3H), 2.74 (dd, J = 17.6, 13.6 Hz, 2H), 2.46 (s, 6H), 2.16 (dd, J =13.6, 7.6 Hz, 1H), 1.93 (dd, J = 13.6, 9.2 Hz, 1H);
13C NMR (100 MHz, CDCl3) δ 179.8, 145.1, 136.5, 136.1, 135.9, 130.4,129.9, 129.6, 128.7, 128.6, 127.4, 127.1, 75.2, 51.7, 51.5, 44.4, 43.4, 32.6,21.7;
HRMS: [M+Na]+ 计算值C33H33NO6S2Na+ 626.1642,实际值626.1640。
1 (400 MHz, CDCl3) δ 8.02 (d, J = 8.4 Hz, 4H), 7.37 (d, J = 8.0 Hz,4H), 4.47 (d, J = 9.2 Hz, 1H), 4.15 (dd, J = 16.0, 9.6 Hz, 1H), 3.55 (d, J =16.0 Hz, 1H), 2.46 (s, 6H), 2.35 (d, J = 12.0 Hz, 2H), 1.24 (s, 3H), 1.06 (s,3H);
13C NMR (100 MHz, CDCl3) δ 174.7, 145.6, 136.2, 129.6, 128.9, 86.6,48.1, 44.2, 38.9, 25.2, 21.7, 21.0;
HRMS: [M+Na]+ 计算值C21H25NO6S2Na+ 474.1016,实际值474.1030。
1(400 MHz, CDCl3) δ 7.98 (d, J = 8.4 Hz, 4H), 7.34 (d, J = 8.4 Hz,4H), 4.01 (d, J = 1.6 Hz, 2H), 2.44 (s, 6H), 2.16 (d, J = 13.6 Hz, 1H), 1.92(d, J = 13.6 Hz, 1H), 1.38 (s, 3H), 1.29 (s, 3H), 1.06 (s, 3H);
13C NMR (100 MHz, CDCl3) δ 180.9, 145.1, 136.8, 129.6, 128.9, 81.8,56.7, 45.4, 40.4, 27.4, 27.1, 26.3, 21.7;
HRMS: [M+Na]+ 计算值C22H27NO6S2Na+ 488.1172,实际值488.1173。
1 (400 MHz, CDCl3) δ 7.91 – 7.74 (m, 3H), 7.31 (td, J = 12.8, 11.2,5.6 Hz, 13H), 7.20 (d, J = 7.2 Hz, 2H), 4.97 (td, J = 9.6, 5.2 Hz, 1H), 4.26(dq, J = 15.2, 8.0, 7.2 Hz, 1H), 3.11 (dd, J = 13.2, 5.2 Hz, 1H), 2.49-2.38(m, 7H), 1.46 – 1.42 (m, 3H).
13C NMR (100 MHz,) δ 175.1, 141.7, 139.1, 129.3, 128.8, 128.7, 128.4,128.3, 128.2, 127.7, 127.3, 127.1, 127.0, 76.2, 61.8, 57.7, 42.0, 21.4, 15.5;
HRMS: [M+Na]+ 计算值C31H31NO6S2Na+ 612.1485,实际值612.1475。
1 (400 MHz, CDCl3) δ 7.95 (d, J = 8.0 Hz, 4H), 7.35 (d, J = 8.0 Hz,4H), 4.57 (dd, J = 10.4, 5.2 Hz, 1H), 4.08 (dd, J = 16.0, 6.8 Hz, 1H), 3.72(dd, J = 15.6, 4.0 Hz, 1H), 2.45 (s, 6H), 2.42 – 2.38 (m, 1H), 2.26 – 2.20(m, 1H), 1.68 (q, J = 11.8 Hz, 1H), 1.01 (s, 9H);
13C NMR (100 MHz, CDCl3) δ 175.5, 145.3, 136.2, 129.7, 128.7, 75.7,51.8, 50.4, 31.7, 29.4, 27.1, 21.7;
HRMS: [M+Na]+ 计算值C23H29NO6S2Na+ 502.1329,实际值502.1336。
1 (400 MHz, CDCl3) δ 7.94 (d, J = 7.6 Hz, 4H), 7.35 (d, J = 7.6 Hz,4H), 4.69-4.60 (m , 1H), 4.01 (dd, J = 15.6, 7.6 Hz, 1H), 3.68 – 3.58 (m,1H), 2.56 – 2.49 (m, 1H), 2.45 (s, 6H), 2.42 – 2.36 (m, 2H), 2.17 – 2.07 (m,1H), 2.05 – 1.95 (m, 4H);
13C NMR (100 MHz, CDCl3) δ 179.9, 145.3, 136.1, 129.7, 128.7, 75.5,51.5, 43.8, 39.0, 31.3, 29.8, 21.7, 16.4;
HRMS: [M+Na]+ 计算值C22H25NO6S2Na+ 486.1016,实际值486.1021。
1 (400 MHz, CDCl3) δ 7.95 (d, J = 8.4 Hz, 4H), 7.36 (d, J = 8.0 Hz,4H), 4.80 – 4.73 (m, 1H), 4.11 (dd, J = 15.6, 7.2 Hz, 1H), 4.02 (dt, J =11.6, 4.4 Hz, 1H), 3.89 (dt, J = 12.4, 4.0 Hz, 1H), 3.71 (dd, J = 15.6, 4.4Hz, 1H), 3.57 – 3.41 (m, 2H), 2.46 (s, 6H), 2.33 (dd, J = 12.8, 6.4 Hz, 1H),2.04 (ddd, J = 13.6, 10.0, 4.0 Hz, 1H), 1.92 – 1.74 (m, 2H), 1.53 – 1.39 (m,2H);
13C NMR (100 MHz, CDCl3) δ 178.6, 145.4, 136.1, 129.7, 128.7, 75.4,63.9, 63.6, 51.8, 41.9, 37.2, 33.6, 32.0, 21.7;
HRMS: [M+Na]+ 计算值C23H27NO7S2Na+ 516.1121,实际值516.1125。
1(400 MHz, CDCl3) δ 7.94 (d, J = 8.4 Hz, 4H), 7.35 (d, J = 8.4 Hz,4H), 4.79 – 4.72 (m, 1H), 4.10 (dd, J = 15.6, 7.2 Hz, 1H), 3.92 (s, 1H), 3.80(s, 1H), 3.71 (dd, J = 15.6, 4.4 Hz, 1H), 3.04 (dt, J = 23.4, 10.6 Hz, 2H),2.45 (s, 6H), 2.24 (dd, J = 13.2, 6.4 Hz, 1H), 1.88 (ddd, J = 13.8, 10.0, 4.0Hz, 1H), 1.79 – 1.69 (m, 2H), 1.51 (dd, J = 15.6, 6.4 Hz, 2H), 1.45 (s, 9H);
13C NMR (100 MHz, CDCl3) δ 178.7, 154.6, 145.5, 136.1, 129.7, 128.7,79.9, 75.5, 51.8, 42.7, 36.6, 33.2, 31.5, 28.4, 21.7;
HRMS: [M+Na]+ 计算值C28H36N2O8S2Na+ 615.1805,实际值615.1812。
1 (400 MHz, CDCl3) δ 8.03 (d, J = 8.4 Hz, 4H), 7.74 (d, J = 7.6 Hz,2H), 7.45 – 7.26 (m, 10H), 5.34 – 5.27 (m, 1H), 4.39 (dd, J = 15.8, 7.2 Hz,1H), 3.98 (dd, J = 15.8, 4.4 Hz, 1H), 2.72 (dd, J = 13.6, 10.4 Hz, 1H), 2.61(dd, J = 13.6, 6.4 Hz, 1H), 2.44 (s, 6H);
13C NMR (100 MHz, CDCl3) δ 175.7, 145.5, 145.4, 144.6, 141.4, 140.6,136.2, 129.8, 129.0, 128.9, 128.8, 128.3, 128.1, 123.6, 122.8, 120.7, 120.4,76.6, 58.5, 52.1, 38.9, 21.7;
HRMS: [M+Na]+ 计算值C31H27NO6S2Na+ 596.1172,实际值596.1177。
1 (400 MHz, CDCl3) δ 7.94 (d, J = 8.0 Hz, 8H), 7.36 (d, J = 8.0 Hz,8H), 5.14-5.07 (m, 2H), 4.08 (dd, J = 15.6, 6.8 Hz, 2H), 3.73 (dd, J = 15.6,5.2 Hz, 2H), 2.66 (dd, J = 13.6, 6.8 Hz, 2H), 2.45 (s, 12H), 2.04 (dd, J =13.2, 8.8 Hz, 2H);
13C NMR (100 MHz, CDCl3) δ 172.0, 145.6, 136.0, 129.9, 128.6, 76.6,52.2, 50.6, 35.7, 21.7;
HRMS: [M+Na]+ 计算值C37H38N2O12S4Na+ 853.1200,实际值853.1205。
1(400 MHz, CDCl3) δ 7.95 (d, J = 7.6 Hz, 4H), 7.36 (d, J = 8.0 Hz,4H), 5.62 (dq, J = 16.8, 7.2 Hz, 1H), 5.21 – 5.11 (m, 2H), 4.91 – 4.82 (m,1H), 4.29 – 4.14 (m, 2H), 4.09 (dd, J = 15.6, 6.8 Hz, 1H), 3.75 – 3.67 (m,1H), 2.73 (dd, J = 14.0, 8.0 Hz, 1H), 2.63 (dd, J = 13.6, 6.0 Hz, 1H), 2.52(dd, J = 14.4, 6.8 Hz, 1H), 2.46 (s, 6H), 1.99 – 1.88 (m, 1H), 1.27 (t, J =7.2 Hz, 3H);
13C NMR (100 MHz, CDCl3) δ 172.6, 168.8, 145.4, 136.1, 131.7, 129.7,128.7, 120.5, 77.2, 62.5, 55.3, 51.4, 38.3, 34.7, 21.7, 14.0;
HRMS: [M+Na]+ 计算值C25H29NO8S2Na+ 558.1222,实际值558.1227。
1 (400 MHz, CDCl3) δ 7.91 (t, J = 7.4 Hz, 4H), 7.50 – 7.27 (m, 9H),4.52 – 4.45 (m, 1H), 4.14 (dd, J = 15.6, 6.0 Hz, 1H), 3.81 (dd, J = 15.6, 5.2Hz, 1H), 2.67 (dd, J = 13.2, 4.8 Hz, 1H), 2.45 (d, J = 5.6 Hz, 6H), 2.06 (dd,J = 13.2, 10.8 Hz, 1H), 2.01 – 1.88 (m, 2H), 0.83- 0.75 (m, 3H);
13C NMR (100 MHz, CDCl3) δ 177.5, 145.3, 137.8, 136.3, 129.7, 128.9,128.6, 127.6, 126.2, 75.1, 53.5, 51.4, 37.2, 32.3, 21.7, 9.0;
HRMS: [M+Na]+ 计算值C27H29NO6S2Na+ 550.1329,实际值550.1336。
1 (400 MHz, CDCl3) δ 8.02 (d, J = 7.6 Hz, 4H), 7.52 – 7.29 (m, 12H),6.88 (s, 2H), 4.49 (t, J = 8.8 Hz, 1H), 4.19 (dd, J = 15.6, 9.2 Hz, 1H), 3.85(d, J = 15.6 Hz, 1H), 3.03 – 2.91 (m, 1H), 2.46 (s, 6H), 1.45 – 1.31 (m, 2H),1.30-1.27 (m, 1H), 1.02 (dt, J = 13.2, 7.2 Hz, 1H), 0.86 (t, J = 6.8 Hz, 3H);
13C NMR (100 MHz, CDCl3) δ 176.5, 145.3, 139.7, 139.2, 136.3, 129.7,128.9, 128.7, 128.6, 128.4, 128.2, 127.8, 127.6, 80.7, 61.3, 52.1, 46.0,31.2, 21.8, 21.5, 14.4;
HRMS: [M+H]+ 计算值C34H35NO6S2Na+ 640.1806,实际值640.1798。
1 (400 MHz, CDCl3) δ 7.88 (t, J = 7.6 Hz, 4H), 7.80-7.13 (m, 10H), ,4.51-4.44 (m, 1H), 4.17 (dd, J = 15.6, 6.4 Hz, 1H), 3.92 (s, 3H), 3.84 (dd, J= 15.6, 5.2 Hz, 1H), 2.74 (dd, J = 13.0, 4.8 Hz, 1H), 2.41 (s, 6H), 2.18 –2.07 (m, 1H), 1.58 (s, 3H);
13C NMR (100 MHz, CDCl3) δ 178.4, 158.1, 145.3, 136.3, 136.1, 133.7,129.7, 129.6, 128.5, 127.9, 124.2, 124.1, 119.4, 105.5, 75.1, 55.4, 49.7,47.9, 41.7, 26.2, 21.7;
HRMS: [M+Na]+ 计算值C31H31NO7S2Na+ 616.1434,实际值616.1439。
1 (400 MHz, CDCl3) δ 7.97 (dd, J = 22.8, 8.4 Hz, 4H), 7.36 (d, J = 8.4Hz, 4H), 4.62 – 4.50 (m, 1H), 4.22 (dd, J = 16.4, 8.4 Hz, 1H), 3.66 (dd, J =16.4, 2.0 Hz, 1H), 2.66 (t, J = 6.0 Hz, 1H), 2.45 (s, 6H), 2.15 (d, J = 13.6Hz, 1H), 2.04 – 0.95 (m, 8H);
13C NMR (100 MHz, CDCl3) δ 176.6, 145.3, 136.3, 129.6, 128.8, 80.7,48.5, 41.6, 38.3, 23.4, 22.6, 22.3, 22.3, 21.7;
HRMS: [M+Na]+ 计算值C23H27NO6S2Na+ 500.1172,实际值500.1174。
实施例23 化合物I-23的合成
向反应烧瓶中加入2,6-二甲氧基-1-碘苯（催化量），间氯过氧苯甲酸（过量），4-甲基-N-甲苯磺酰基苯磺酰胺（过量），六氟异丙醇中溶解。然后再加入2-乙烯基苯甲酸II-23（2 mmol）。反应混合物室温条件下继续搅拌7小时。通过薄层色谱检测反应过程。反应完成后，加入碱调节pH，乙酸乙酯萃取，低温减压蒸馏去除溶剂。所得残渣经柱层析纯化，得到5-氨基-γ-内酯类化合物I-23（白色固体，收率75%，0.71克）。该产物为新化合物，结构经1HNMR, 13C NMR，HRMS确证。
1 (400 MHz, CDCl3) δ 8.03 (d, J = 8.4 Hz, 4H), 7.91 (d, J = 7.6 Hz,1H), 7.67 (t, J = 7.4 Hz, 1H), 7.57 (t, J = 7.4 Hz, 1H), 7.51 (d, J = 7.6 Hz,1H), 7.39 (d, J = 8.0 Hz, 4H), 5.82 (dd, J = 8.4, 2.8 Hz, 1H), 4.10 (dd, J =16.0, 8.8 Hz, 1H), 3.96 (dd, J = 16.0, 3.2 Hz, 1H), 2.47 (s, 6H);
13C NMR (100 MHz, CDCl3) δ 169.4, 146.2, 145.5, 136.1, 134.3, 130.0,129.8, 128.8, 126.2, 126.1, 122.5, 80.0, 52.3, 21.8;
HRMS: [M+Na]+ 计算值C23H21NO6S2Na+ 494.0703,实际值494.0707。
实施例24 化合物I-24的合成
向反应烧瓶中加入2,6-二甲氧基-1-碘苯（催化量），间氯过氧苯甲酸（过量），4-甲基-N-甲苯磺酰基苯磺酰胺（过量），六氟异丙醇中溶解。然后再加入2-乙烯基-1-萘甲酸II-24（2 mmol）。反应混合物室温条件下继续搅拌7小时。通过薄层色谱检测反应过程。反应完成后，加入碱调节pH，乙酸乙酯萃取，低温减压蒸馏去除溶剂。所得残渣经柱层析纯化，得到5-氨基-γ-内酯类化合物I-24（白色固体，收率70%，0.73克）。该产物为新化合物，结构经1HNMR, 13C NMR，HRMS确证。
1(400 MHz, CDCl3) δ 8.21 (d, J = 7.2 Hz, 1H), 8.16 (d, J = 8.0 Hz,4H), 8.05 (dd, J = 14.8, 8.0 Hz, 2H), 7.88 (d, J = 8.4 Hz, 1H), 7.82 – 7.75(m, 2H), 7.44 (d, J = 7.6 Hz, 4H), 6.25 (d, J = 9.2 Hz, 1H), 4.39 (d, J =16.0 Hz, 1H), 4.01 (dd, J = 16.0, 9.6 Hz, 1H), 2.50 (s, 6H);
13C NMR (100 MHz, CDCl3) δ 169.8, 145.8, 145.4, 136.3, 131.3, 129.7,129.6, 129.3, 129.1, 128.9, 128.4, 126.9, 124.2, 124.0, 120.7, 80.5, 53.1,21.6;
HRMS: [M+Na]+ 计算值C27H23NO6S2Na+ 544.0859,实际值544.0848。
实施例25 ~ 28的方法步骤同实施例23，合成得到化合物I-25 ~ I-28
1H NMR (400 MHz, CDCl3) δ 7.99 (d, J = 8.0 Hz, 4H), 7.59 – 7.45 (m,3H), 7.38 (d, J = 8.0 Hz, 4H), 5.80 (d, J = 5.2 Hz, 1H), 4.11 (dd, J = 16.0,8.4 Hz, 1H), 3.94 (dd, J = 16.0, 2.8 Hz, 1H), 2.48 (s, 6H);
13C NMR (100 MHz, CDCl3) δ 168.1 (168.1) ,164.8 (162.3), 145.5, 141.8(141.7), 136.1, 129.7, 128.8, 128.4 (128.3), 124.5 (124.4), 122.3 (122.1),112.6 (112.3), 79.8, 52.2, 21.7;
HRMS: [M+Na]+ 计算值C23H20FNO6S2Na+ 512.0608,实际值512.0599。
1 (400 MHz, CDCl3) δ 7.98 (d, J = 8.4 Hz, 4H), 7.86 (s, 1H), 7.58 (d,J = 8.4 Hz, 1H), 7.44 (d, J = 8.0 Hz, 1H), 7.38 (d, J = 8.4 Hz, 4H), 5.80(dd, J = 8.0, 3.6 Hz, 1H), 4.11 (dd, J = 16.0, 8.4 Hz, 1H), 3.93 (dd, J =16.0, 3.6 Hz, 1H), 2.47 (s, 6H);
13C NMR (100 MHz, CDCl3) δ 167.9, 145.6, 144.4, 136.4, 136.0, 134.5,129.8, 128.7, 127.9, 125.88, 124.1, 79.7, 52.0, 21.8;
HRMS: [M+Na]+ 计算值C23H20ClNO6S2Na+ 528.0313,实际值528.0304。
1 (400 MHz, CDCl3) δ 7.93 (d, J = 8.4 Hz, 4H), 7.54 (s, 1H), 7.35 (d,J = 8.4 Hz, 4H), 7.11 (s, 2H), 6.39 (dd, J = 12.8, 3.2 Hz, 1H), 4.20 (dd, J =15.6, 12.8 Hz, 1H), 3.84 (s, 3H), 2.83 (dd, J = 15.6, 3.2 Hz, 1H), 2.46 (s,6H);
13C NMR (100 MHz, CDCl3) δ 163.3, 159.3, 145.5, 136.9, 129.8, 129.5,128.7, 128.6, 125.2, 122.2, 113.1, 85.8, 55.7, 32.5, 21.8;
HRMS: [M+Na]+ 计算值C24H23NO7S2Na+ 524.0808,实际值524.0805。
1 (400 MHz, CDCl3) δ 7.99 (d, J = 7.6 Hz, 4H), 7.85 (d, J = 7.6 Hz,1H), 7.70 (t, J = 7.6 Hz, 1H), 7.58 – 7.51 (m, 2H), 7.35 (d, J = 8.0 Hz, 4H),4.28 (d, J = 16.0 Hz, 1H), 4.13 (d, J = 16.0 Hz, 1H), 2.45 (s, 6H), 1.53 (s,3H);
13C NMR (100 MHz, CDCl3) δ 168.7, 151.2, 145.1, 136.7, 134.3, 129.8,129.5, 128.9, 126.2, 125.9, 121.9, 86.3, 56.3, 23.5, 21.7;
HRMS: [M+Na]+ 计算值C24H23NO6S2Na+ 508.0859, 实际值 508.0866。
对比例1 采用4-硝基碘苯作为催化剂进行实施例1
向反应烧瓶中加入4-硝基碘苯（催化量），间氯过氧苯甲酸（过量），4-甲基-N-甲苯磺酰基苯磺酰胺（过量），乙腈中溶解。然后再加入2,2-苯基-4-戊烯酸II-1（2 mmol）。反应混合物室温条件下继续搅拌24小时。通过薄层色谱检测反应过程。反应完成后，加入碱调节pH，乙酸乙酯萃取，低温减压蒸馏去除溶剂。所得残渣经柱层析纯化，得到5-氨基-γ-内酯类化合物I-1（白色固体，收率8%，0.092克）。
对比例2 采用过氧化氢作为氧化剂进行实施例1
向反应烧瓶中加入2,6-二甲氧基-1-碘苯（催化量），过氧化氢（过量），4-甲基-N-甲苯磺酰基苯磺酰胺（过量），乙腈中溶解。然后再加入2,2-苯基-4-戊烯酸II-1（2 mmol）。反应混合物室温条件下继续搅拌24小时。通过薄层色谱检测反应过程。反应完成后，加入碱调节pH，乙酸乙酯萃取，低温减压蒸馏去除溶剂。所得残渣经柱层析纯化，无法得到5-氨基-γ-内酯类化合物I-1。
对比例3 采用乙醇作为溶剂进行实施例1
向反应烧瓶中加入2,6-二甲氧基-1-碘苯（催化量），过氧化氢（过量），4-甲基-N-甲苯磺酰基苯磺酰胺（过量），乙醇中溶解。然后再加入2,2-苯基-4-戊烯酸II-1（2 mmol）。反应混合物室温条件下继续搅拌24小时。通过薄层色谱检测反应过程。反应完成后，加入碱调节pH，乙酸乙酯萃取，低温减压蒸馏去除溶剂。所得残渣经柱层析纯化，得到5-氨基-γ-内酯类化合物I-1（白色固体，收率15%，0.173克）。
对比例4 采用4-甲氧基苯磺酰胺作为氮源进行实施例1
向反应烧瓶中加入2,6-二甲氧基-1-碘苯（催化量），过氧化氢（过量），4-甲氧基苯磺酰胺（过量），乙醇中溶解。然后再加入2,2-苯基-4-戊烯酸II-1（2 mmol）。反应混合物室温条件下继续搅拌24小时。通过薄层色谱检测反应过程。反应完成后，加入碱调节pH，乙酸乙酯萃取，低温减压蒸馏去除溶剂。所得残渣经柱层析纯化，得到5-氨基-γ-内酯类化合物（白色固体，收率20%，0.168克）。
上述实施例并非是对于本发明的限制，本发明并非仅限于上述实施例，只要符合本发明要求，均属于本发明的保护范围。

Claims (2)

1.一种5-氨基-γ-内酯衍生物的合成方法，其特征在于：以结构式(II)所示的4-戊烯酸类化合物为底物，采用2,6-二甲氧基-1-碘苯/间氯过氧苯甲酸催化体系，苯磺酰亚胺类化合物为氮源，室温反应构建结构式(I)所示的5-氨基-γ-内酯衍生物，
R1和R2独立地选自氢、C1～C7的烷基、C2～C5的烷基羧基、苯基或取代的苯基、苄基或取代的苄基、萘基或取代的萘基，所述取代的苯基、取代的苄基或取代的萘基中的取代基为C1～C5的烷基、C1～C5的烷氧基、卤素、硝基、三氟甲基、C1～C7的酯基、C4～C10的杂环基，所述杂环基为氧杂环、氮杂环、硫杂环；
或R1和R2形成C3～C6的环烷基、C3～C6的杂环基、取代的C4～C15的环烷基、或取代的C4～C15的杂环基；
R3选自氢、C1～C7的烷基、苯基、苄基；
或R1、R2和R3形成C4～C5的环烷基，C4～C5的杂环基，取代的C4～C15的环烷基，取代的C4～C15的杂环基或取代的C4～C15的苯并基，所述取代的C4～C15的环烷基，取代的C4～C15的杂环基或取代的C4～C15的苯并基中的取代基为C1～C7的烷基、卤素、硝基、三氟甲基，C4～C6的环烷基；
R4和R5独立地选自氢、C1～C5的烷基、苯基、苄基；
R6选自苯基或取代的苯基，所述取代的苯基中的取代基为C1～C5的烷基、C1～C5的烷氧基、硝基、三氟甲基、卤素。
2.根据权利要求1所述的5-氨基-γ-内酯衍生物的合成方法，其特征在于：所述苯磺酰亚胺类化合物选自4-甲基-N-甲苯磺酰基苯磺酰胺、4-硝基-N-((4-硝基苯基)磺酰基)苯磺酰胺、N-(苯磺酰基)苯磺酰胺。
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