通过1-磷杂富烯合成含磷多环化合物

引用本文: 申宁宁, 刘艳杰, 田荣强, 段征, MatheyFrancois. 通过1-磷杂富烯合成含磷多环化合物[J]. 有机化学, 2019, 39(8): 2277-2286. doi: 10.6023/cjoc201903042 shu

Citation: Shen Ningning, Liu Yanjie, Tian Rongqiang, Duan Zheng, Mathey Francois. Synthesis of Polycyclic Phosphacycles via 1-Phosphafulvene[J]. Chinese Journal of Organic Chemistry, 2019, 39(8): 2277-2286. doi: 10.6023/cjoc201903042 shu

通过1-磷杂富烯合成含磷多环化合物

郑州大学化学与分子工程学院国际磷化学实验室河南省有机磷功能分子国际联合实验室郑州 450001

通讯作者: 田荣强, tianrq@zzu.edu.cn; 段征, duanzheng@zzu.edu.cn

基金项目:

国家自然科学基金(Nos.21302174, 21672193, 21272218)、中国博士后科学基金(No.2017M622362)、郑州大学优秀青年发展基金(No.1621316006)资助项目

摘要: 1-磷杂富烯能够以2π、4π、6π体系参与环加成反应，并转化为多种磷杂多环化合物.报道了1-磷杂富烯和对苯醌以及N-苯基马来酰亚胺在加热条件下反应合成磷杂多环产物的新方法.研究结果表明对苯醌与1-磷杂富烯通过氧化加成反应产生一个易发生Diels-Alder反应的磷杂环戊烯中间体.该中间体与2分子N-苯基马来酰亚胺经过两次Diels-Alder反应形成磷杂多环化合物.研究还表明1-磷杂富烯环外双键对该反应的发生至关重要.

关键词:

English

Synthesis of Polycyclic Phosphacycles via 1-Phosphafulvene

International Phosphorus Laboratory, International Joint Research Laboratory for Functional Organophosphorus Materials of Henan Province, College of Chemistry and Molecular Engineering, Zhengzhou University, Zhengzhou 450001

Corresponding author: Tian, Rongqiang, E-mail: tianrq@zzu.edu.cn; Duan, Zheng, E-mail: duanzheng@zzu.edu.cn

Received Date: 21 March 2019
Revised Date: 11 April 2019
Available Online: 25 August 2019
Fund Project:

Project supported by the National Natural Science Foundation of China (Nos. 21302174, 21672193, 21272218), the China Postdoctoral Science Foundation(No. 2017M622362), and the Young Talent Research Fund of Zhengzhou University (No. 1621316006)

Abstract: 1-Phosphafulvenes are unique in their cycloaddition reactions, which act as 2π, 4π, and 6π systems and provide versatile and powerful approaches to various polycyclic systems. The reaction of 1-phosphafulvene with 1, 4-benzoquinone and N-phenylmaleimide upon heating provided phosphapolycyclic rings in moderate to good yields. The possible mechanism included an oxidative addition of 1-phosphafulvene with 1, 4-benzoquinone and successive Diels-Alder reactions with N-phenylmaleimide. The exocyclic C=C bond of 1-phosphafulvene is cruial to this reaction.

Key words:

富烯^[1]分子含有三个共轭的碳碳双键, 因此环外双键的电子可迁移到环内, 并使富烯分子具有类似环戊二烯阴离子的芳香性和较大的偶极矩(1~5.5 D).富烯的结构特征还决定了其反应的多样性:具有芳香性的富烯五元环骨架可用来合成茂金属配合物^[2]; 三个共轭碳碳双键, 能够以[2+2]、[2+4]、[4+2]、[4+3]、[6+2]、[6+3]、[6+4]等形式发生环加成反应^[3], 并用于多环体系和天然产物的合成^[4].

有机磷化合物与相应含碳类似物存在许多相似的反应性能^[5], 这在低配位的亚磷烯和C＝P双键上表现得尤为明显, 并吸引了众多化学研究者的兴趣^[6].磷杂乙烯中C＝P键基本上是非极性的, 计算表明, C＝P的π键键能为180 kJ/mol低于乙烯中C＝C的键能(272 kJ/mol).因此, C＝P双键的反应活性要高于C＝C双键, 许多含C＝P双键的化合物不太稳定, 容易通过C＝P双键发生反应.我们发现通过磷杂环戊二烯和醛亚胺可一步合成α-C₂-桥联双磷杂环戊二烯1^[7], 其反应机理中涉及1-磷杂富烯2的[6+6]环加成反应. α-C₂-桥联双磷杂环戊二烯1可以在高温下原位生成1-磷杂富烯2, 1-磷杂富烯和富烯一样也具有丰富的环加成反应模式, 既可作为富电的4π体系发生[4+2]环加成反应, 也可通过活性更高的C＝P双键以2π体系发生[2+4]环加成反应, 还能以6π体系发生[6+4]和[6+6]环加成反应(Scheme 1)^[8]. 1, 4-对苯醌在有机合成中即可作为氧化剂参与氧化反应, 也可作为缺电子烯烃用于环加成反应^[9].本研究将通过1-磷杂富烯和对苯醌之间的反应, 来进一步揭示磷杂富烯的化学性质.

图式 1

图式 1. 1-磷杂富烯的环加成反应

Scheme 1. Cycloadditions of 1-phosphafulvenes

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1. 结果与讨论

直接利用α-C₂-桥联双磷杂环戊二烯1作为磷杂富烯前体与对苯醌不发生反应.于是我们参考文献方法将1转化为另一种磷杂富烯前体1-磷杂降冰片烯衍生物3a~3e (Eq. 1)^[8].化合物3a和对苯醌在100 ℃下反应仅生成少量新的含磷化合物, 同时剩余大量3a.产物4a经过柱色谱分离, 并通过单晶衍射分析确认了结构(图 1).晶体结构揭示了4a分子中含有两个N-苯基马来酰亚胺结构单元, 因此我们尝试在反应中补加N-苯基马来酰亚胺来促进反应进行完全.经优化, 当补加1.3 equiv. N-苯基马来酰亚胺时, 反应可以顺利完成(Scheme 2), 同时产率提高为67%.

图 1

图 1. 化合物4a的晶体结构

Figure 1. X-ray crystal structure of 4a

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图式 2

图式 2. 1-磷杂降冰片烯3和对苯醌以及N-苯基马来酰亚胺的反应

Scheme 2. Reaction of 1-phosphanorbornenes 3 with 1, 4-ben- zoquinone and N-phenylmaleimide

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(1)

在以前Hong等关于酰氯对富烯的氧化加成^[10]基础上, 我们推测该反应可能按照Scheme 3中所示路线进行:首先1-磷杂降冰片烯3原位热解为1-磷杂富烯2, 随后和对苯醌发生反应得到中间体5, 磷杂环戊烯衍生物5和N-苯基马来酰亚胺发生Diels-Alder反应得到并环的磷杂环戊烯衍生物6, 磷杂环戊烯衍生物6再次和N-苯基马来酰亚胺发生Diels-Alder反应得到产物4.

图式 3

图式 3. 可能的反应机理

Scheme 3. Proposed mechanism

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在化合物2到化合物5的转变过程中, 1-磷杂富烯2的环外双键并未发生改变.那么具有类似骨架结构的2H-磷杂环戊二烯是否能够和对苯醌发生类似的氧化加成反应呢? 2H-磷杂环戊二烯8在室温下易发生自身的Diels-Alder反应得到二聚体7, 二聚体7在加热下可以原位生成2H-磷杂环戊二烯8^[11].我们通过文献方法合成了2H-磷杂环戊二烯的二聚体7, 但遗憾的是原位热解产生的2H-磷杂环戊二烯8并没有和1, 4-对苯醌发生反应(Scheme 4).这说明1-磷杂富烯的环外双键对和1, 4-苯醌反应的发生至关重要.

图式 4

图式 4. 2H-磷杂环杂环戊二烯和1, 4-苯醌的反应

Scheme 4. Reaction of 2H-phosphole with 1, 4-benzoquinone

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在上述研究结果的基础上, 我们研究了1-磷杂富烯环外双键上的取代基团对反应的影响.当1-磷杂富烯环外双键的苯环上连有吸电子基团(4b, 4c)时有利于反应发生, 产率比连有给电子基团(4a)时明显提高(Eq. 2).

(2)

当1, 4-苯醌上连有取代基团时, 反应需要在更高的温度(140~200℃)下进行, 且产率下降. 1, 4-苯醌上连有一个取代基时, 会生成两个区域选择性产物10da和11da, 反应的产率和选择性受位阻影响较大.例如, 当R'为位阻小的氯原子时(表 1, Entries 1, 4), 10和11的产率相当, 当R'为位阻较大的OMe时(Entry 3), 只有R'远离桥环的产物10dc生成.从10bb晶体结构上可以看出, 对苯醌上的甲基在产物上处于远离磷原子的一侧(图 2). 2, 3, 5, 6-四氯-1, 4-苯醌仍可以和1-磷杂富烯发生反应, 在200 ℃时以45%的产率得到多环产物12 (Eq. 3).但当使用位阻更大的3-甲基-2, 6-二甲氧基-1, 4-苯醌或2, 6-二叔丁基基-1, 4-苯醌时, 即使在200 ℃的高温下反应也不会发生.

(3)

表 1

表 1 1, 4-苯醌的适用范围

Table 1. Substrate scope of 1, 4-benzoquinone

下载: 导出CSV


Entry	Ar	R'	T/℃	Yield/%
Entry	Ar	R'	T/℃	10	11
1	Ph(3d)	Cl (9a)	170	28 (10da)	27 (11da)
2	Ph(3d)	Me (9b)	200	39 (10db)	13 (11db)
3	Ph(3d)	OMe (9c)	200	35 (10dc)	0 (11dc)
4	2-ClC₆H₄ (3b)	Cl (9a)	140	34 (10ba)	32 (11ba)
5	2-ClC₆H₄ (3b)	Me (9b)	200	45 (10bb)	15 (11bb)
6	4-CH₃C₆H₄ (3a)	Me (9b)	200	34 (10ab)	12 (11ab)

图 2

图 2. 化合物10bb的晶体结构

Figure 2. X-ray crystal structure of 10bb

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2. 结论

综上所述, 1-磷杂降冰片烯衍生物3作为1-磷杂富烯2的前体, 在加热条件下和对苯醌、N-苯基马来酰亚胺以较高的产率反应生成复杂的含磷多环化合物.研究表明通过1, 4-苯醌对1-磷杂富烯的氧化加成反应, 产生了一个易发生Diels-Alder反应的磷杂环戊烯中间体.该中间体通过与两分子的N-苯基马来酰亚胺经过两次Diels-Alder反应构筑了磷杂多环化合物. 1-磷杂富烯的环外双键对该反应的发生至关重要, 无环外双键的2H-磷杂环戊二烯8不能与对苯醌发生类似的反应.

3. 实验部分

3.1 仪器与试剂

所有实验均是在氮气氛围下进行的, 反应溶剂均在氮气氛围下按标准方法进行无水处理.核磁共振谱用Bruker公司300 MHz核磁共振仪测定; 高分辨质谱(HRMS)用Agilent公司1290-6540 UHPLC Q-Tof型质谱仪测定; X单晶衍射数据通过Oxford diffraction Gemini E单晶仪测定.层析用硅胶(200~300目)由青岛海洋化工厂购买.化合物1^[7]和3^[8]参考文献方法制备.其他商品化试剂购买后直接使用, 未再进一步纯化

3.2 实验方法

3.2.1 化合物3c和3e的合成

在75 mL干燥的厚壁耐压管中, 加入联磷杂环戊二烯1(5 mmol)、N-苯基马来酰亚胺(15 mmol, 2.6 g)、甲苯(30 mL), 加热到170 ℃反应44 h, 取出耐压管缓慢恢复至室温, 核磁磷谱检测反应完成.使用旋转蒸发仪除掉溶剂甲苯, 剩下的混合物通过柱色谱分离[洗脱剂: V(乙酸乙酯):V(石油醚)＝1:10]得到白色固体1-磷杂降冰片烯衍生物3.

1-磷杂降冰片烯3c: 3.41 g, 产率67%, endo:exo＝50:7. ¹H NMR (300 MHz, CDCl₃) δ: 1.92 (s, 3H, CH₃), 2.02 (s, 3H, CH₃), 3.19 (d, J＝8.1 Hz, 1H, CH), 3.80~3.87 (m, 1H, CH), 6.41 (d, J＝19.2 Hz, 1H, ＝CH), 6.91~6.94 (m, 2H, Ph), 7.16~7.49 (m, 10H, Ph), 7.48 (d, J＝2.0 Hz, 1H, Ph), 7.67 (s, 1H, Ph); ¹³C NMR (75 MHz, CDCl₃) δ: 15.35 (s, CH₃), 16.10 (s, CH₃), 45.17 (d, J_CP＝24.6 Hz, CH), 50.59 (s, CH), 65.09 (d, J_CP＝6.0 Hz, C), 121.71 (d, J_CP＝16.4 Hz, ＝CH), 122.60 (s, C), 126.66 (s, PhCH), 127.31 (s, PhCH), 127.59 (d, J_CP＝10.4 Hz, PhCH), 128.52 (s, PhCH), 128.60 (s, PhCH), 128.70 (s, PhCH), 129.20 (s, PhCH), 130.03 (s, PhCH), 130.97 (s, PhCH), 131.71 (s, C), 131.85 (d, J_CP＝8.7 Hz, PhCH), 136.76 (d, J_CP＝21.3 Hz, ＝C), 138.08 (s, C), 140.90 (d, J_CP＝20.8 Hz, ＝C), 153.25 (d, J_CP＝1.7 Hz, C), 157.51 (d, J_CP＝11.5 Hz, ＝C), 174.92 (s, CO), 175.04 (s, CO); ³¹P NMR (CDCl₃, 121 MHz) δ: －27.7. HRMS calcd for C₂₉H₂₄BrNO₂P (M+H⁺) 528.0726, found528.0726.

1-磷杂降冰片烯衍生物endo-3e: 2.03 g, 产率47%. ¹H NMR (300 MHz, CDCl₃) δ: 1.90 (s, 3H, CH₃), 2.00 (s, 3H, CH₃), 3.19 (d, J＝8.1 Hz, 1H, CH), 3.73~3.85 (m, 1H, CH), 6.58 (d, J＝20.1 Hz, 1H, ＝CH), 6.91~6.94 (m, 3H, Ar), 7.11 (s, 1H, Ar), 7.24~7.32 (m, 9H, Ar); ¹³C NMR (75 MHz, CDCl₃) δ: 15.42 (s, CH₃), 16.12 (s, CH₃), 45.46 (d, J_CP＝24.7 Hz, CH), 50.93 (s, CH), 64.92 (d, J_CP＝6.0 Hz, C), 116.39 (d, J_CP＝19.1 Hz, ＝CH), 126.61 (s, ArCH), 127.29 (s, ArCH), 128.54 (s, ArCH), 128.69 (s, ArCH), 128.79 (s, ArCH), 129.22(s, ArCH), 129.39 (s, ArCH), 131.81 (s, ArC), 136.92 (d, J_CP＝22.4 Hz, ＝C), 140.04 (s, ArC), 140.61 (d, J_CP＝21.3 Hz, ＝C), 153.56 (s, ArC), 153.96 (d, J_CP＝11.0 Hz, ＝C), 175.01 (s, CO), 175.13 (s, CO); ³¹P NMR (CDCl₃, 121 MHz) δ: －27.8. HRMS calcd forC₂₇H₂₃NO₂PS (M+H⁺) 456.1182, found 456.1185.

1-磷杂降冰片烯衍生物exo-3e: 0.71g, 产率15%. ¹H NMR (300 MHz, CDCl₃) δ: 1.90 (s, 3H, CH₃), 2.00 (s, 3H, CH₃), 3.18 (d, J＝7.8 Hz, 1H, CH), 3.82 (t, J＝8.7 Hz, 1H, CH), 6.59 (d, J＝20.1 Hz, 1H, ＝CH), 6.93 (s, 3H, Ar), 7.12 (s, 1H, Ar), 7.24~7.30 (m, 9H, Ar); ¹³C NMR (75 MHz, CDCl₃) δ: 15.35 (s, CH₃), 16.08 (s, CH₃), 45.46 (d, J_CP＝24.6 Hz, CH), 50.91 (s, CH), 64.90 (d, J_CP＝6.1 Hz, C), 116.34 (d, J_CP＝19.7 Hz, ＝CH), 126.53 (s, ArCH), 127.13 (s, ArCH), 127.20 (s, Ar, CH), 128.46 (s, ArCH), 128.64 (s, ArCH), 128.74 (s, ArCH), 129.17 (s, ArCH), 131.69 (s, ArC), 136.84 (d, J_CP＝21.3 Hz, ＝C), 139.94 (s, ArC), 140.61 (d, J_CP＝20.8 Hz, ＝C), 153.48 (s, ArC), 153.89 (d, J_CP＝11.5 Hz, ＝C), 174.96 (s, CO), 175.10 (s, CO); ³¹P NMR (CDCl₃, 121 MHz) δ: －27.7. HRMS calcd for C₂₇H₂₃NO₂PS (M+H⁺) 456.1182, found 456.1185.

3.2.2 化合物4a~4e的合成

在35 mL干燥的厚壁耐压管中, 室温下依次加入1-磷杂降冰片烯衍生物3a~3e (0.5 mmol)、对苯醌(0.6 mmol, 65 mg)和N-苯基马来酰亚胺(0.65 mmol, 113 mg)、5 mL甲苯, 搅拌均匀后将耐压管放入油浴中加热至100 ℃反应48 h后, 取出耐压管缓慢恢复至室温, 通过核磁磷谱检测反应完成.使用旋转蒸发仪除掉甲苯, 剩下的混合物通过柱色谱分离提纯得到黄色固体4[先用二氯甲烷分离出N-苯基马来酰亚胺, 再逐渐梯度洗脱至V(二氯甲烷):V(甲醇)＝300:1].化合物4a的晶体通过二氯甲烷和乙醚(V:V＝1:1)混合溶剂缓慢挥发得到.

磷杂多环化合物4a: 255 mg, 产率67%. m.p. 195~196 ℃; ¹H NMR (300 MHz, CDCl₃) δ: 1.68 (s, 3H, CH₃), 2.53 (d, J＝12.0 Hz, 1H, CH), 3.31 (d, J＝14.1 Hz, 1H, CH), 3.47 (s, 2H, CH₂), 3.76 (s, 3H, CH₃) 4.36 (d, J＝7.5 Hz, 1H, CH), 4.46 (d, J＝22.8 Hz, 1H, CH), 5.35 (s, 1H, OH), 6.21 (d, J＝7.5 Hz, 2H Ph), 6.36 (s, 2H Ph), 6.80 (d, J＝7.8 Hz, 2H Ph), 7.08 (d, J＝6.6 Hz, 2H Ph), 7.25~7.43 (m, 11H Ph), 7.63 (t, J＝7.8 Hz, 4H Ph); ¹³C NMR (75 MHz, CDCl₃) δ: 13.35 (s, CH₃), 23.55 (s, CH₂), 40.98 (s, CH), 42.59 (s, CH), 44.08 (s, CH), 47.36 (s, CH), 50.51 (s, CH), 55.33 (s, OCH₃), 59.10 (d, J_CP＝24.1 Hz, C), 67.64 (d, J_CP＝13.7 Hz, C), 113.31 (s, PhCH), 115.87 (s, PhCH), 119.40 (s, PhCH), 126.65(s, PhCH), 127.23 (s, PhCH), 128.07 (s, C), 128.55 (s, PhCH), 128.90 (s, Ph, CH), 128.90 (s, Ph, CH), 129.28 (s, Ph, CH), 129.49 (s, Ph, CH), 130.84 (d, J_CP＝20.8 Hz, C), 131.74 (s, C), 132.15 (s, C), 133.21 (s, PhCH), 135.30 (s, C), 135.58 (s, C), 148.50 (s, C), 151.79 (s, C), 159.19 (s, C), 175.70 (s, CO), 175.93 (s, CO), 177.57 (s, CO), 178.34 (s, CO); ³¹P NMR (CDCl₃, 121 MHz) δ: 118.0. HRMS calcd for C₄₆H₃₈N₂O₇P (M+ H⁺) 761.2417, found 761.2406.

磷杂多环化合物4b: 367 mg, 产率96%. m.p. 210~211 ℃; ¹H NMR (300 MHz, (CD₃)₂SO) δ: 1.62 (s, 3H, CH₃), 3.22 (d, J＝14.7 Hz, 1H, CH), 3.67 (s, 2H, CH₂), 3.91 (d, J＝4.8 Hz, 1H, CH), 4.56 (d, J＝3.0 Hz, 1H, CH), 4.95 (d, J＝20.1 Hz, 1H, CH), 6.42 (d, J＝39.9 Hz, 4H, Ph), 7.09~7.57 (m, 18H, Ph), 7.83 (s, 1H, Ph), 9.19 (s, 1H, OH); ¹³C NMR (75 MHz, (CD₃)₂SO)δ: 13.43 (s, CH₃), 23.73 (s, CH₂), 42.56 (s, CH), 47.39 (s, CH), 50.80 (s, CH), 58.02 (d, J_CP＝31.7 Hz, C), 66.24 (d, J_CP＝11.0 Hz, C), 116.22 (s, PhCH), 119.75 (s, PhCH), 119.85 (s, Ph, CH), 126.43 (s, PhCH), 127.09 (s, Ph, CH), 127.14 (s, Ph, CH), 127.35 (s, PhCH), 127.51 (s, PhCH), 128.79 (s, PhCH), 129.19 (s, PhCH), 129.30 (s, PhCH), 129.65 (s, PhCH), 129.74 (s, PhCH), 129.87 (s, PhCH), 130.14 (s, PhCH), 131.79 (d, J_CP＝19.0 Hz, C), 132.51 (s, C), 132.75 (s, PhCH), 132.98 (s, C), 134.47 (s, C), 134.94 (d, J_CP＝25.1 Hz, C), 135.23 (s, C), 136.11 (d, J_CP＝6.5 Hz, C), 147.63 (d, J_CP＝6.1 Hz, C), 153.66 (s, C), 175.15 (s, CO), 175.70 (d, J_CP＝1.6 Hz, CO), 177.41 (s, CO), 178.35 (s, CO) (2.5处有一个氢, 40处有两个C被溶剂(CD₃)₂SO覆盖); ³¹P NMR ((CD₃)₂SO, 121 MHz) δ: 114.9. HRMS calcd for C₄₅H₃₅ClN₂O₆P (M+H⁺) 809.1416, found 809.1409.

磷杂多环化合物4c: 323 mg, 产率84%. m.p. 206~207 ℃; ¹H NMR (300 MHz, (CD₃)₂SO) δ: 1.58 (s, 3H, CH₃), 3.17 (d, J＝14.7 Hz, 1H, CH), 3.59~3.70 (m, 2H, CH₂), 3.80 (d, J＝7.8 Hz, 1H, CH), 4.42~4.49 (m, 2H, CH), 6.19 (d, J＝8.4 Hz, 2H, Ph), 6.43 (d, J＝8.1 Hz, 2H, Ph), 7.11 (d, J＝7.5 Hz, 2H, Ph), 7.24~7.31 (m, 4H, Ph), 7.39~7.57 (m, 11H, Ph), 7.76 (d, J＝7.5 Hz, 1H, Ph), 8.11 (s, 1H, Ph), 9.14 (s, 1H, OH). ¹³C NMR (75 MHz, (CD₃)₂SO)δ: 18.02 (s, CH₃), 28.64 (d, J_CP＝3.8 Hz, CH₂), 45.91 (s, CH), 47.31 (s, CH), 49.06 (s, CH), 52.25 (s, CH), 55.50 (s, CH), 63.15 (d, J_CP＝26.3 Hz, C), 71.47 (d, J_CP＝14.3 Hz, C), 120.74 (s, PhCH), 124.62(s, PhCH), 124.70 (s, Ph, CH), 126.31 (s, C), 132.01 (s, PhCH), 132.05 (s, Ph, CH), 132.31 (s, PhCH), 133.51 (s, PhCH), 133.65 (s, PhCH), 133.92 (s, PhCH), 134.12 (s, PhCH), 134.41 (s, PhCH), 134.51 (s, PhCH), 134.79 (s, PhCH), 135.31 (s, PhCH), 135.77 (s, PhCH), 136.57 (d, J_CP＝22.5 Hz, C), 137.27 (s, C), 137.82 (s, C), 138.86 (s, J_CP＝25.2 Hz, C), 139.13 (s, Ph, CH), 141.03 (d, J_CP＝6.5 Hz, C), 145.55 (s, C), 152.28 (d, J_CP＝6.0 Hz, C), 158.22 (s, C), 180.37 (s, CO), 180.57 (s, CO), 182.84 (s, CO), 183.28 (s, CO) (2.5处有一个氢被(CD₃)₂SO覆盖); ³¹P NMR ((CD₃)₂SO, 121 MHz) δ: 116.9. HRMS calcd for C₄₅H₃₅BrN₂O₆P (M+H⁺) 809.1416, found 809.1409.

磷杂多环化合物4d: 250 mg, 产率70%. m.p. 195.5~196.3 ℃; ¹H NMR (300 MHz, CDCl₃) δ: 1.69 (s, CH₃), 2.54 (d, J＝9.9 Hz, 1H, CH), 3.31 (d, J＝14.7 Hz, 1H, CH), 3.49 (s, 2H, CH₂), 3.90 (d, J＝7.5 Hz, 1H, CH), 4.36 (d, J＝7.2 Hz, 1H, CH), 4.50 (d, J＝21.3 Hz, 1H, CH), 6.20 (d, J＝7.5 Hz, 2H, Ph), 6.36 (d, J＝7.5 Hz, 2H, Ph) 7.08 (d, J＝6.0 Hz, 2H, Ph), 7.30~7.55 (m, 14H, Ph), 7.62 (d, J＝5.7 Hz, 2H, Ph), 7.70 (d, J＝13.5 Hz, 2H, CH); ¹³C NMR (75 MHz, CDCl₃) δ: 13.23 (s, CH₃), 23.58 (s, CH₂), 40.92 (s, CH), 43.40 (d, J_CP＝4.4 Hz, CH), 43.86 (s, CH), 47.28 (s, CH), 50.45 (s, CH), 58.83 (d, J_CP＝25.57 Hz, C), 67.59 (d, J_CP＝13.1 Hz, C), 115.82 (s, PhCH), 119.37 (s, PhCH), 119.47 (s, Ph, CH), 126.51 (s, PhCH), 127.12 (s, PhCH), 127. 86 (s, PhCH), 127.96 (s, PhCH), 128.44 (s, PhCH), 128.78 (s, Ph, CH), 128.96 (s, PhCH), 129.19 (s, PhCH), 129.34 (s, PhCH), 129.48 (s, PhCH), 129.61 (s, PhCH), 130.63 (d, J_CP＝22.4 Hz, C), 131.65 (s, C), 131.92 (s, PhCH), 132.08 (s, C), 135.43 (d, J_CP＝5.0 Hz, C), 135.64 (d, J_CP＝13.7 Hz, C), 135.96 (s, C), 148.61 (s, C), 151.52 (s, C), 175.41 (s, CO), 175.74 (s, CO), 177.18 (s, CO), 177.96 (s, CO); ³¹P NMR (CDCl₃, 121 MHz) δ: 119.3. HRMS calcd for C₄₅H₃₆N₂O₆P (M+H⁺) 731.2311, found 731.2307.

磷杂多环化合物4e: 202 mg, 产率55%. m.p. 194~195 ℃; ¹H NMR (300 MHz, (CD₃)₂SO) δ: 1.56 (s, CH₃), 3.14 (d, J＝14.7 Hz, 1H, CH), 3.61~3.78 (m, 2H, CH₂), 4.06 (d, J＝8.1 Hz, 1H, CH), 4.51 (d, J＝7.8 Hz, 1H, CH), 4.75 (dd, ¹J＝21.0 Hz, ²J＝4.2 Hz, 1H, CH), 6.16 (d, J＝8.7 Hz, 2H, Ar), 6.42 (d, J＝8.7 Hz, 2H, Ar), 7.01 (t, J＝3.9 Hz, 1H, Ar), 7.13 (d, J＝7.2 Hz, 2H, Ar), 7.28 (d, J＝8.1 Hz, 3H, Ar), 7.32~7.57 (m, 12H, Ar), 9.14 (s, 1H, OH); ¹³C NMR (75 MHz, (CD₃)₂SO) δ: 13.18 (s, CH₃), 23.91 (s, CH₂), 37.17 (d, J_CP＝4.5 Hz, CH), 40.87 (s, CH), 44.32 (s, CH), 47.63 (s, CH), 50.74 (s, CH), 59.20 (d, J_CP＝24.6 Hz, C), 66.75 (d, J_CP＝14.3 Hz, C), 115.90 (s, ArCH), 120.10 (s, ArCH), 120.19 (s, Ar, CH), 125.89 (s, ArCH), 126.91 (s, ArCH), 127.26 (s, ArCH), 127.30 (s, Ar, CH), 127.57 (s, ArCH), 128.71 (s, ArCH), 128.90 (s, ArCH), 129.14 (s, ArCH), 129.36 (s, ArCH), 129.65 (s, ArCH), 130.09 (s, ArCH), 131.58 (d, J_CP＝22.4 Hz, C), 132.57 (s, C), 133.08 (s, C), 133.84 (d, J_CP＝24.6 Hz, C), 136.40 (d, J_CP＝6.0 Hz, C), 139.72 (s, C), 147.81 (d, J_CP＝6.1 Hz, C), 153.43 (s, C), 175.82 (s, CO), 175.92 (s, CO), 177.69 (s, CO), 178.60 (s, CO) (2.5处有一氢, 40处有一个碳被(CD₃)₂SO覆盖); ³¹P NMR ((CD₃)₂SO, 121 MHz) δ: 124.4. HRMS calcd for C₄₃H₃₄N₂O₆PS (M+H⁺) 737.1875, found 737.1867.

3.2.3 化合物10、11、12的合成

在35 mL干燥的厚壁耐压管中, 室温下依次加入1-磷杂降冰片烯衍生物3a, 3b或3d (0.5 mmol)、取代对苯醌(0.6 mmol)和N-苯基马来酰亚胺(0.65 mmol, 113 mg)、5 mL甲苯, 搅拌均匀后将耐压管放入油浴中加热到反应温度, 然后保持温度反应48 h, 取出耐压管缓慢恢复至室温, 通过核磁磷谱检测反应完成.使用旋转蒸发仪除掉溶剂甲苯, 剩下的混合物通过柱色谱分离提纯得到黄色固体10和11或12[先用二氯甲烷分离出N-苯基马来酰亚胺, 再逐渐梯度洗脱至V(二氯甲烷):V(甲醇)＝300:1].化合物10bb的晶体结构在乙酸乙酯溶液中缓慢挥发得到.

磷杂多环化合物10da:反应温度: 170 ℃, 107 mg, 产率28%. ¹H NMR (300 MHz, CDCl₃) δ: 1.70 (s, 3H, CH₃), 2.54 (d, J＝11.1 Hz, 1H, CH), 3.32 (d, J＝14.1 Hz, 1H, CH), 3.49 (s, 2H, CH₂), 3.87 (d, J＝7.5 Hz, 1H, CH), 4.32 (d, J＝7.5 Hz, 1H, CH), 4.50 (d, J＝22.8 Hz, 1H, CH) 6.20 (d, J＝8.1 Hz, 1H, Ph), 6.27 (s, 1H, OH), 6.62 (d, J＝8.4 Hz, 1H, Ph), 7.09 (d, J＝5.7 Hz, 2H, Ph), 7.24~7.44 (m, 15H, Ph), 7.62 (d, J＝6.0 Hz, 2H, Ph), 6.74 (d, J＝4.5 Hz, 2H, Ph); ³¹P NMR (CDCl₃, 121 MHz) δ: 117.6; ¹³C NMR (75 MHz, CDCl₃) δ: 13.23 (s, CH3), 23.59 (s, CH₂), 40.89 (s, CH), 43.27 (d, J_CP＝3.8 Hz, CH), 43.69 (d, J_CP＝2.3 Hz, CH), 47.18 (s, CH), 50.39 (s, CH), 58.92 (d, J_CP＝25.2 Hz, C), 67.51 (d, J_CP＝12.6 Hz, C), 116.37 (s, PhCH), 118.52 (s, PhCH), 118.62 (s, Ph, CH), 119.46 (s, Ph, CH), 119.56 (s, PhCH), 119.63 (s, C), 126.40 (s, PhCH), 126.44 (s, Ph, CH), 126.44 (s, Ph, CH), 126.50 (s, Ph, CH), 127.36 (s, PhCH), 127.39 (s, Ph, CH), 127.99 (s, PhCH), 128.60 (s, PhCH), 128.77 (s, PhCH), 128.98 (s, PhCH), 129.20 (s, PhCH), 129.35 (s, PhCH), 129.42 (s, PhCH), 129.56 (s, PhCH), 130.71 (d, J_CP＝23.0 Hz, C), 131.64 (s, C), 131.95 (s, PhCH), 132.10 (s, C), 135.30 (d, J_CP＝6.6 Hz, C), 135.60 (d, J_CP＝24.0 Hz, C), 135.88 (s, C), 147.40 (s, C), 148.54 (d, J_CP＝6.1 Hz, C), 175.19 (d, J_CP＝2.2 Hz, CO), 175.55 (s, CO), 176.96 (s, CO), 177.81 (s, CO). HRMS calcd forC₄₅H₃₅ClN₂O₆P (M+H⁺) 765.1921, found 765.1920.

磷杂多环化合物11da:反应温度: 170 ℃, 96 mg, 产率27%. ¹H NMR (300 MHz, CDCl₃) δ: 1.65 (s, 3H, CH₃), 2.54 (d, J＝8.4 Hz, 1H, CH), 3.27 (d, J＝14.7 Hz, 1H, CH), 3.36~3.55 (m, 2H, CH₂), 4.00 (d, J＝7.8 Hz, 1H, CH), 4.45 (dd, J＝21.3 Hz, J＝4.5 Hz, 1H, CH), 4.60 (d, J＝8.1 Hz, 1H, CH), 6.18 (dd, ¹J＝8.7 Hz, ²J＝2.4 Hz, 1H, Ph), 6.27 (s, 1H, OH), 6.47 (d, J＝2.4 Hz, 1H, Ph), 6.70 (d, J＝8.7 Hz, 1H, Ph), 7.06~7.43 (m, 17H, Ph), 7.62 (d, J＝7.2 Hz, 3H, Ph); ¹³C NMR (75 MHz, CDCl₃) δ: 13.29 (s, CH₃), 23.70 (s, CH₂), 40.76 (s, CH), 43.21 (d, J_CP＝5.5 Hz, CH), 43.91 (d, J_CP＝2.3 Hz, CH), 48.02 (s, CH), 50.60 (s, CH), 59.28 (d, J_CP＝25.1 Hz, C), 67.25 (d, J_CP＝11.0 Hz, C), 114.36 (s, PhCH), 116.95 (s, PhCH), 118.01 (s, Ph, CH), 118.22 (s, PhCH), 123.90 (s, C), 126.55 (s, PhCH), 126.59 (s, Ph, CH), 127.12 (s, PhCH), 127.15 (s, Ph, CH), 127.76 (s, PhCH), 128.01 (s, PhCH), 128.25 (s, PhCH), 129.01 (s, PhCH), 129.31 (s, Ph, CH), 129.39 (s, Ph, CH), 129.53 (s, Ph, CH), 129.68 (s, Ph, CH), 130.30 (d, J_CP＝23.0 Hz, C), 131.19 (s, PhCH), 131.62 (s, C), 132.08 (s, C), 134.90 (d, J_CP＝6.0 Hz, C), 135.93 (s, C), 136.17 (d, J_CP＝24.6 Hz, C), 144.67 (d, J_CP＝5.0 Hz, C), 151.11 (s, C), 175.45 (s, CO), 175.78 (s, CO), 177.52 (s, CO), 178.06 (s, CO); ³¹P NMR (CDCl₃, 121 MHz) δ: 111.5. HRMS calcd for C₄₅H₃₅ClN₂O₆P (M+H⁺) 765.1921, found 765.1920.

磷杂多环化合物10db和11db:反应温度: 200 ℃, 193 mg, 产率52% (10db:11db＝3:1, 两个产物的比例根据核磁氢谱确定). ¹H NMR (300 MHz, CDCl₃) δ: 1.75 (s, CH₃), 1.94 (s, CH₃), 2.65 (s, J＝15.9 Hz, 1H, CH), 3.38 (d, J＝14.7 Hz, 1H, CH), 3.54~3.72 (m, 2H, CH₂), 4.06 (d, J＝8.4 Hz, 1H, CH), 4.52 (d, J＝8.1 Hz, 1H, CH), 5, 22 (dd, J＝20.4, 4.8 Hz, 1H, CH), 6.18 (d, J＝2.4 Hz, 1H, Ph), 6.27~6.31 (m, 1H, Ph), 6.37~6.40 (m, 1H, Ph), 7.06~7.49 (m, 16H, Ph), 7.66 (d, J＝7.5 Hz, Ph), 7.90 (d, J＝7.8 Hz, Ph); ¹³C NMR (75 MHz, CDCl₃) δ: 13.41 (s, CH₃), 15.75 (s, CH₃), 23.51 (s, CH₂), 39.63 (d, J_CP＝2.3 Hz, CH), 40.47 (s, CH), 42.19 (s, CH), 47.03 (s, CH), 50.46 (s, CH), 58.05 (d, J_CP＝31.2 Hz, C), 67.17 (d, J_CP＝12 Hz, C), 115.39 (s, PhCH), 116.83 (s, PhCH), 116.91 (s, Ph, CH), 121.38 (s, PhCH), 121.48 (s, Ph, CH), 125.05 (s, C), 126.06 (s, PhCH), 126.33 (s, PhCH), 126.39 (s, Ph, CH), 126.55 (s, PhCH), 127.15 (s, PhCH), 128.41 (s, PhCH), 128.58 (s, PhCH), 128.91 (s, PhCH), 128.97 (s, PhCH), 129.33 (s, PhCH), 129.66 (s, PhCH), 129.80 (s, PhCH), 130.03 (s, PhCH), 131.59 (s, C), 132.00 (s, C), 132.67 (s, PhCH), 133.91 (s, C), 134.78 (s, C), 135.41 (d, J_CP＝6.0 Hz, C), 136.21 (d, J_CP＝24.6 Hz, C), 148.28 (d, J_CP＝5.4 Hz, C), 149.84 (s, C), 175.01 (s, CO), 175.32 (d, J_CP＝2.2 Hz, CO), 176.84 (s, CO), 177.85 (s, CO); ³¹P NMR (CDCl₃, 121 MHz) δ: 114.6. HRMS calcd for C₄₆H₃₈N₂O₆P (M+H⁺) 745.2462, found 745.2467.

磷杂多环化合物10dc: 133 mg, 反应温度200 ℃, 产率35%. ¹H NMR (300 MHz, CDCl₃) δ: 1.70 (s, CH₃), 2.54~2.59 (m, 1H, CH), 3.33 (d, J＝14.7 Hz, 1H, CH), 3.46 (s, 3H, CH₃), 3.46~3.57 (m, 2H, CH₂), 3.93 (d, J＝8.1 Hz, 1H, CH), 4.38 (d, J＝8.1 Hz, 1H, CH), 5.53 (dd, J＝21.9, 4.2 Hz, 1H, CH), 5.96~5.98 (m, 2H, Ph), 6.58 (d, J＝9.0 Hz, 1H, Ph), 7.09 (m, 1H, Ph), 7.09 (d, J_CP＝7.2 Hz, 2H, Ph), 7.28~7.47 (m, 14H, Ph), 7.65 (d, J＝7.5 Hz, 2H, Ph), 7.76~7.78 (m, 2H, Ph).¹³C NMR (75 MHz, CDCl₃) δ: 13.23 (s, CH₃), 23.48 (s, CH₂), 40.87 (s, CH), 40.60 (d, J_CP＝4.9 Hz, CH), 44.05 (s, CH), 47.73 (s, CH), 50.75 (s, CH), 54.95 (s, ℃H₃) 58.79 (d, J_CP＝25.7 Hz, C), 67.88 (d, J_CP＝15.8Hz, C), 105.87 (s, PhCH), 120.18 (s, Ph, CH), 126.50 (s, PhCH), 126.56 (s, Ph, CH), 126.61 (s, Ph, CH), 126.66 (s, Ph, CH), 127.56 (s, PhCH), 127.86 (s, PhCH), 126.55 (s, PhCH), 128.72 (s, PhCH), 128.91 (s, PhCH), 129.14 (s, PhCH), 129.64 (s, PhCH), 129.78 (s, PhCH), 130.29 (d, J_CP＝23.0 Hz, C), 131.71 (s, PhCH), 131.74 (s, C), 132.25 (s, C), 135.68 (s, C), 135.80 (d, J_CP＝30.1 Hz, C), 136.21 (s, C), 137.43 (d, J_CP＝3.3 Hz, C), 150.60 (d, J_CP＝1.1 Hz, C), 152.10 (s, C), 175.01 (d, J_CP＝1.7 Hz, CO), 175.94 (d, CO), 177.09 (s, CO), 178.03 (s, CO); ³¹P NMR (CDCl₃, 121 MHz) δ: 118.1. HRMS calcd for C₄₆H₃₈N₂O₇P (M+H⁺) 761.2417, found 761.2413.

磷杂多环化合物10ba:反应温度: 140 ℃, 139.6 mg, 产率34%. ¹H NMR (300 MHz, CDCl₃) δ: 1.72 (s, 3H, CH₃), 2.65 (d, J＝9.9 Hz, 1H, CH), 3.37 (d, J＝14.4 Hz, 1H, CH), 3.55~3.74 (m, 2H, CH₂), 4.15 (d, J＝7.8 Hz, 1H, CH), 4.72 (d, J＝7.5 Hz, 1H, CH), 5.19 (dd, J＝20.4, 3.0 Hz, 1H, CH), 5.76 (s, 1H, OH), 6.20 (d, J＝7.2 Hz, 1H, CH), 6.57 (s, 1H, CH), 6.76 (d, J＝8.4 Hz, 1H, Ph), 6.85 (t, J＝7.2 Hz, 1H Ph), 7.05~7.43 (m, 15H, Ph), 7.59 (d, J＝7.5 Hz, 1H, Ph), 7.66 (d, J＝6.9 Hz, 2H, Ph); ¹³C NMR (75 MHz, CDCl₃) δ: 13.45 (s, CH₃), 23.71 (s, CH₂), 39.58 (d, J_CP＝3.75 Hz, CH), 40.45 (s, CH), 42.33 (s, CH), 47.62 (s, CH), 50.45 (s, CH), 58.10 (d, J_CP＝30.6 Hz, C), 67.15 (d, J_CP＝10.4 Hz, C), 114.50 (s, PhCH), 117.06 (s, PhCH), 118.44 (s, PhCH), 118.64 (s, Ph, CH), 123.95 (s, C), 126.28 (s, PhCH), 126.42 (s, Ph, CH), 126.48 (s, Ph, CH), 126.54(s, Ph, CH), 127.21 (s, PhCH), 128.26 (s, PhCH), 128.79 (s, PhCH), 128.86 (s PhCH), 129.00 (s, PhCH), 129.18 (s, PhCH), 129.38 (s, PhCH), 129.66 (s, PhCH), 129.81 (s, PhCH), 130.03 (s, PhCH), 130.53 (d, J_CP＝23.5 Hz, C), 131.54 (s, C), 131.97 (s, C), 132.0 (s, PhCH), 133.61 (s, C), 134.54 (s, C), 134.73 (d, J_CP＝6.0 Hz, C), 136.93 (d, J_CP＝24.6 Hz, C), 144.29 (d, J_CP＝5.0 Hz, C), 151.47 (s, C), 175.00 (s, CO), 175.36 (d, J_CP＝1.7 Hz, CO), 177.50 (s, CO), 177.98 (s, CO); ³¹P NMR (CDCl₃, 121 MHz) δ: 112.1. HRMS calcd for C₄₅H₃₅Cl₂- N₂O₆P (M+H⁺) 799.1532, found 799.1531

磷杂多环化合物11ba:反应温度140 ℃, 127.68 mg, 产率32%. ¹H NMR (300 MHz, CDCl₃) δ: 1.76 (s, 3H, CH₃), 2.65 (d, J＝9.3 Hz, 1H, CH), 3.38 (d, J＝14.4 Hz, 1H, CH), 3.54~3.71 (m, 2H, CH₂), 4.04 (d, J＝7.8 Hz, 1H, CH), 4.50 (d, J＝8.1 Hz, 1H, CH), 5.23 (dd, ¹J＝20.7 Hz, ²J＝4.2 Hz, 1H, CH), 6.40~6.44 (m, 2H, Ph), 6.68 (d, J＝8.4 Hz, 1H, Ph), 7.06~7.15 (m, 3H, Ph), 7.23~7.50 (m, 13H, Ph), 7.66 (d, J＝7.5 Hz, 2H, Ph), 7.79 (d, J＝7.8 Hz, 1H, Ph); ¹³C NMR (75 MHz, CDCl₃) δ: 13.39 (s, CH₃), 23.54 (s, CH₂), 39.49 (d, J_CP＝2.7 Hz, CH), 40.39 (s, CH), 42.10 (d, J_CP＝1.5 Hz, CH), 47.02 (d, J_CP＝2.3 Hz, CH), 50.40 (s, CH), 58.11 (d, J_CP＝31.1 Hz, C), 67.03 (d, J_CP＝11.5 Hz, C), 116.51 (s, PhCH), 118.64 (s, Ph, CH), 118.81 (s, Ph, CH), 118.90 (s, PhCH), 119.56 (s, PhCH), 119.66 (s, Ph, CH), 119.75 (s, C), 125.99 (s, PhCH), 126.20 (s, PhCH), 126.25 (s, Ph, CH), 126.50 (s, PhCH), 127.44 (s, PhCH), 128.56 (s, PhCH), 128.63 (s, PhCH), 128.94 (s, Ph, CH), 129.00 (s, Ph, CH), 129.04 (s, Ph, CH), 129.22 (s, PhCH), 129.33 (s, PhCH), 129.44 (s, PhCH), 129.50 (s, PhCH), 129.64 (s, PhCH), 130.11 (s, PhCH), 130.84 (d, J_CP＝24.1 Hz, C), 131.56 (s, C), 131.97 (s, C), 132.40 (s, PhCH), 133.79 (s, C), 134.87 (s, C), 135.05 (d, J_CP＝3.0 Hz, C), 136.43 (d, J_CP＝24.6 Hz, C), 147.55 (s, C), 148.40 (d, J_CP＝5.5 Hz, C), 174.76 (s, CO), 175.02 (d, J_CP＝2.3 Hz, CO), 176.74 (s, CO), 177.68 (s, CO); ³¹P NMR (CDCl₃, 121 MHz) δ: 108.6. HRMS calcd for C₄₅H₃₅Cl₂N₂O₆P (M+H⁺) 799.1532, found 799.1531.

磷杂多环化合物10bb:反应温度170 ℃, 175 mg, 产率45%. ¹H NMR (300 MHz, (CD₃)₂SO) δ: 1.66 (s, 3H, CH₃), 1.87 (s, 3H, CH₃), 3.24 (d, J＝13.8 Hz, 1H, CH), 3.69 (s, 2H, CH₂), 3.93 (d, J＝6.3 Hz, 1H, CH), 4.57 (d, J＝6.9 Hz, 1H, CH), 4.98 (d, J＝20.4 Hz, 1H, CH), 6.14 (s, 1H, Ph), 6.30 (s, 1H, Ph), 6.54 (d, J＝7.2 Hz, 1H, Ph), 7.10~7.60 (m, 18H, Ph), 7.88 (d, J＝6.3 Hz, 1H, Ph), 9.09 (s, 1H, OH); ¹³C NMR (75 MHz, (CD₃)₂SO) δ: 13.45 (s, CH₃), 16.41 (s, CH₃), 23.69 (s, CH₂), 42.54 (s, CH), 47.33 (s, CH), 50.82 (s, CH), 57.95 (d, J_CP＝31.7 Hz, C), 66.26 (d, J_CP＝12.1 Hz, C), 115.39 (s, PhCH), 116.68 (s, PhCH), 116.76 (s, Ph, CH), 121.20 (s, PhCH), 116.76 (s, Ph, CH), 125.29 (s, C), 126.42 (s, PhCH), 127.08 (s, PhCH), 127.13 (s, Ph, CH), 127.31 (s, PhCH), 127.51 (s, PhCH), 128.77 (s, PhCH), 129.14 (s, PhCH), 129.31 (s, PhCH), 129.65 (s, PhCH), 129.80 (s, PhCH), 129.93 (s, PhCH), 130.12 (s, PhCH), 131.85 (d, J_CP＝23.6 Hz, C), 132.50 (s, C), 132.83 (s, PhCH), 132.97 (s, C), 134.48 (s, C), 134.88 (d, J_CP＝24.6 Hz, C), 135.24 (s, C), 136.21 (d, J_CP＝6.0 Hz, C), 147.37 (d, J_CP＝6.0 Hz, C), 151.65 (s, C), 175.18 (s, C＝O), 175.71 (s, C＝O), 177.32 (s, C＝O), 178.34 (s, C＝O)(2.5处有一个氢, 40处有两个碳被(CD₃)₂SO覆盖); ³¹P NMR ((CD₃)₂SO, 121 MHz) δ: 114.7. HRMS calcd for C₄₇H₄₀ClN₂O₇P (M+H⁺) 775.2568, found 775.2573.

磷杂多环化合物11bb:反应温度170 ℃, 58 mg, 产率15%. ¹H NMR (300 MHz, CDCl₃) δ: 1.57 (s, 3H, CH₃), 1.72 (s, 3H, CH₃), 3.22 (d, J＝14.7 Hz, 1H, CH), 3.70 (s, 2H, CH₂), 3.96 (d, J＝7.5 Hz, 1H, CH), 4.60 (d, J＝7.8 Hz, 1H, CH), 4.93 (d, J＝20.1 Hz, 1H, CH), 6.25 (d, J＝8.1 Hz, 1H, Ph), 6.44 (s, 1H, Ph), 6.72~6.83 (m, 2H, Ph), 7.08 (d, J＝6.9 Hz, 1H, Ph), 7.25~7.63 (m, 16H, Ph), 9.00 (s, 1H, OH); ¹³C NMR (75 MHz, CDCl₃) δ: 13.44 (s, CH₃), 16.40 (s, CH₃), 23.69 (s, CH₂), 42.52 (s, CH), 47.32 (s, CH), 50.81 (s, CH), 57.94 (d, J_CP＝31.1 Hz, C), 66.26 (d, J_CP＝12.1 Hz, C), 115.36 (s, PhCH), 116.72 (d, J_CP＝6.5 Hz, PhCH), 121.24 (d, J_CP＝8.2 Hz, PhCH), 125.27 (s, C), 126.41 (s, PhCH), 127.12 (s, PhCH), 127.31 (s, PhCH), 127.50 (s, PhCH), 128.76 (s, PhCH), 129.13 (s, PhCH), 129.30 (s, PhCH), 129.64 (s, PhCH), 129.79 (s, PhCH), 129.93 (s, PhCH), 130.11 (s, PhCH), 131.85 (d, J_CP＝23.0 Hz, C), 132.49 (s, C), 132.82 (s, PhCH), 132.96 (s, C), 134.47 (s, C), 134.86 (d, J_CP＝24.6 Hz, C), 135.24 (s, C), 136.21 (d, J_CP＝6.0 Hz, C), 147.36 (d, J_CP＝6.0 Hz, C), 151.65 (s, C), 175.15 (s, CO), 175.71 (s, CO), 177.32 (s, CO), 178.33 (s, CO) (2.5处有一个氢, 40处有两个碳被(CD₃)₂SO覆盖); ³¹P NMR (CDCl₃, 121 MHz) δ: 111.0. HRMS calcd for C₄₇H₄₀ClN₂O₇P (M+H⁺) 775.2568, found 775.2573

磷杂多环化合物10ab:反应温度200 ℃, 131.58 mg, 产率34%. ¹H NMR (300 MHz, CDCl₃) δ: 1.67 (s, 3H, CH₃), 1.88 (s, 3H, CH₃), 2.46 (d, J＝9.6 Hz, 1H, CH), 3.25 (d, J＝14.4 Hz, 1H, CH), 3.32~3.43 (m, 2H, CH₂), 3.73 (s, 3H, ℃H₃), 3.87 (d, J＝7.8 Hz, 1H, CH), 4.32 (d, J＝8.1 Hz, 1H, CH), 4.41 (dd, ¹J＝22.2 Hz, ²J＝3.9 Hz, 1H, Ph), 5.99 (s, 1H, OH), 6.08 (d, J＝8.7 Hz, 1H, Ph), 6.20 (d, J＝8.7 Hz, 1H, Ph), 6.82 (d, J＝8.4 Hz, 2H, Ph), 7.06 (d, J＝7.2 Hz, 2H, Ph), 7.20~7.40 (m, 12H, Ph), 7.63 (t, J＝9.0 Hz, 4H, Ph); ¹³C NMR (75 MHz, CDCl₃) δ: 13.25 (s, CH₃), 15.86 (s, CH₃), 23.47 (s, CH₂), 40.97 (s, CH), 42.63 (s, CH), 44.00 (s, CH), 47.24 (s, CH), 50.52 (s, CH), 55.27 (s, CH), 59.00 (d, J_CP＝25.1 Hz, C), 67.71 (d, J_CP＝13.7 Hz, C), 113.24 (s, PhCH), 115.24 (s, PhCH), 116.46 (s, PhCH), 116.55 (s, Ph, CH), 121.19 (s, PhCH), 121.29 (s, Ph, CH), 125.03 (s, C), 126.61 (s, PhCH), 127.13 (s, PhCH)128.05 (s, C), 128.47 (s, PhCH), 128.77 (s, PhCH), 129.03 (s, PhCH), 129.15 (s, PhCH), 129.39 (s, PhCH), 129.60 (s, PhCH), 129.74 (s, PhCH), 130.88 (d, J_CP＝23.0 Hz, C), 131.70 (s, C), 132.16 (s, C), 133.27 (s, PhCH), 135.31 (d, J_CP＝24.6 Hz, C), 135.75 (d, J_CP＝6.0 Hz, C), 148.30 (d, J_CP＝5.6 Hz, C), 149.87 (s, C), 159.17 (s, C), 175.60 (s, CO), 175.90 (s, CO), 177.37 (s, CO), 178.22 (s, CO); ³¹P NMR (CDCl₃, 121 MHz) δ: 118.9. HRMS calcd forC₄₇H₄₀ClN₂O₇P (M+H⁺) 775.2568, found 775.2573.

磷杂多环化合物11ab:反应温度200 ℃, 36 mg, 产率12%. ¹H NMR (300 MHz, CDCl₃) δ: 1.59 (s, 3H, CH₃), 1.66 (s, 3H, CH₃), 2.56 (d, J＝13.5 Hz, 1H, CH), 3.33 (d, J＝14.4 Hz, 1H, CH), 3.46~3.57 (m, 2H, CH₂), 3.69 (s, 3H, ℃H₃), 3.92 (d, J＝7.8 Hz, 1H, CH), 4.38~4.50 (m, 2H, CH), 6.32 (d, J＝8.4 Hz, 1H, Ph), 6.40 (s, 1H, OH), 6.61 (d, J＝8.4 Hz, 2H, Ph), 6.73 (d, J＝8.1 Hz, 1H, Ph), 7.10 (d, J＝8.4 Hz, 2H, Ph), 7.20~7.32 (m, 4H, Ph), 7.43~7.51 (m, 8H, Ph), 7.57 (d, J＝8.4 Hz, 2H, Ph), 7.65 (d, J＝7.5 Hz, 2H, Ph); ¹³C NMR (75 MHz, CDCl₃) δ: 13.25 (s, CH₃), 15.86 (s, CH₃), 23.47 (s, CH₂), 40.97 (s, CH), 42.63 (s, CH), 44.00 (s, CH), 47.24 (s, CH), 50.52 (s, CH), 55.27 (s, CH), 59.00 (d, J_CP＝25.1 Hz, C), 67.71 (d, J_CP＝13.7 Hz, C), 113.24 (s, PhCH), 115.24 (s, PhCH), 116.46 (s, PhCH), 116.55 (s, Ph, CH), 121.19 (s, PhCH), 121.29 (s, Ph, CH), 125.03 (s, C), 126.61 (s, PhCH), 127.13 (s, PhCH)128.05 (s, C), 128.47 (s, PhCH), 128.77 (s, PhCH), 129.03 (s, PhCH), 129.15 (s, PhCH), 129.39 (s, PhCH), 129.60 (s, PhCH), 129.74 (s, PhCH), 130.88 (d, J_CP＝23.0 Hz, C), 131.70 (s, C), 132.16 (s, C), 133.27 (s, PhCH), 135.31 (d, J_CP＝24.6 Hz, C), 135.75 (d, J_CP＝6.0 Hz, C), 148.30 (d, J_CP＝5.6 Hz, C), 149.87 (s, C), 159.17 (s, C), 175.60 (s, CO), 175.90 (s, CO), 177.37 (s, CO), 178.22 (s, CO); ³¹P NMR (CDCl₃, 121 MHz) δ: 111.1. HRMS calcd for C₄₇H₄₀ClN₂O₇P (M+H⁺) 775.2568, found 775.2573.

磷杂多环化合物12:反应温度200 ℃, 194.8 mg, 产率45%. ¹H NMR (300 MHz, CDCl₃) δ: 1.74 (s, 3H, CH₃), 2.73~2.75 (m, 1H, CH), 3.34 (d, J＝15.9 Hz, 1H, CH), 3.42~3.85 (m, 2H, CH₂), 4.32 (d, J＝8.1 Hz, 1H, CH), 4.51 (dd, J＝15.9 Hz, J＝5.7 Hz, 1H, CH), 4.66 (d, J＝7.8 Hz, 1H, CH), 7.01~7.50 (m, 18H, Ph), 7.64 (d, J＝7.8 Hz, 1H, Ph). ¹³C NMR (75 MHz, CDCl₃) δ: 13.47 (s, CH₃), 22.97 (s, CH₂), 39.53 (s, CH), 39.27 (t, J_CP＝20.25 Hz, CH), 42.98 (s, CH), 48.55 (s, CH), 51.34 (s, CH), 61.56 (d, J_CP＝32.3 Hz, C), 66.70 (d, J_CP＝12.5 Hz, C), 119.85 (s, C), 119.99 (s, C), 123.92 (s, C), 126.51 (s, PhCH), 127.25 (s, PhCH), 128.02 (s, PhCH), 128.18 (s, PhCH), 128.74 (s, PhCH), 128.97 (s, PhCH), 129.09 (s, PhCH), 129.34 (s, PhCH), 129.53 (s, C), 129.78 (s, PhCH), 129.85 (s, Ph, CH), 129.91 (s, Ph, CH), 130.77 (s, PhCH), 131.70 (s, C), 131.97 (s, C), 134.49 (d, J_CP＝5.5 Hz, C), 136.04 (d, J_CP＝26.3 Hz, C), 136.93 (s, C), 142.19 (s, C), 143.79 (s, C), 145.99 (s, C), 175.18 (s, C＝O), 175.88 (s, C＝O), 176.77 (s, C＝O), 178.01 (s, C＝O); ³¹P NMR (CDCl₃, 121 MHz) δ: 112.75. HRMS calcd for C₄₅H₃₂Cl₄- N₂O₆P (M+H⁺) 867.0752, found 867.0744.

辅助材料(Supporting Information) 化合物3, 4, 10, 11, 12的核磁谱图, 化合物4a (CCDC 1865443)和10bb (CCDC 1865440)的单晶结构数据.这些材料可以免费从本刊网站(http://si℃-journal.cn/)上下载.

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图式 1 1-磷杂富烯的环加成反应

Scheme 1 Cycloadditions of 1-phosphafulvenes

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图 1 化合物4a的晶体结构

Figure 1 X-ray crystal structure of 4a

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图式 2 1-磷杂降冰片烯3和对苯醌以及N-苯基马来酰亚胺的反应

Scheme 2 Reaction of 1-phosphanorbornenes 3 with 1, 4-ben- zoquinone and N-phenylmaleimide

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图式 3 可能的反应机理

Scheme 3 Proposed mechanism

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图式 4 2H-磷杂环杂环戊二烯和1, 4-苯醌的反应

Scheme 4 Reaction of 2H-phosphole with 1, 4-benzoquinone

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图 2 化合物10bb的晶体结构

Figure 2 X-ray crystal structure of 10bb

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表 1 1, 4-苯醌的适用范围

Table 1. Substrate scope of 1, 4-benzoquinone


Entry	Ar	R'	T/℃	Yield/%
Entry	Ar	R'	T/℃	10	11
1	Ph(3d)	Cl (9a)	170	28 (10da)	27 (11da)
2	Ph(3d)	Me (9b)	200	39 (10db)	13 (11db)
3	Ph(3d)	OMe (9c)	200	35 (10dc)	0 (11dc)
4	2-ClC₆H₄ (3b)	Cl (9a)	140	34 (10ba)	32 (11ba)
5	2-ClC₆H₄ (3b)	Me (9b)	200	45 (10bb)	15 (11bb)
6	4-CH₃C₆H₄ (3a)	Me (9b)	200	34 (10ab)	12 (11ab)

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