English

• 1.   Introduction

  As an important class of N-heterocycle, quinazolines have attracted much attention due to their prevalence in natural products and pharmaceuticals.^[1] Consequently, great efforts have been made for the syntheses of quinazoline scaffolds.^[2] The common methods include condensation of o-carbonyl anilines with benzylamines, oxime ether or aldehydes in the presence of ammonia equivalents, ^[3] condensation of o-aminobenzylamines with various carbon sources, ^[4] and cyclization of o-halobenzyl halides, o-halo- benzyl aldehydes, o-halobenzoic acids, or o-halobenzyl- amines with amidines or other reagents.^[5] Alternatively, coupling of amidines with alkynes, dimethyl sulfoxide (DMSO), aldehydes, or paraformaldehyde has also proved to be successful.^[6] With the advancement of C—H activation, intramolecular annulation of arylamidines via oxidative C—C bond formation and intermolecular C—H functionalization of benzimidates with dioxazolones or azides has been realized.^[7] Moreover, the utilization of o-nitro- acetophenone, diaryliodonium salts, aryldiazonium salts or other substrates has also been reported to prepare quinazolines.^[8] Oxidation reactions have been recognized as one of the most important strategies in organic syntheses. Meanwhile, earth-abundant transition metal-catalyzed reactions have also witnessed a rapid growth in assembly of new chemical bonds.^[9] Considering green and sustainable chemistry, the appropriate choice of low toxic metal coupled with readily available oxygen or air as an oxidant would provide new opportunities in modern synthetic chemistry.^[10] Phthalocyanine is a planar large conjugated system composed of four large indole units, moreover, phathalocyanine metal complexes (MPcs) (Scheme 1) are known to activate oxygen to fulfil various oxidation reactions.^[11] For instance, the group of Bäckvall, ^[12] Taniguchi, ^[13] Knölker, ^[14] and others^[15] have contributed to MPcs-catalyzed defunctionalisation of alkenes, oxidative coupling of various substrates, and other aerobic oxidation reactions. While above respectable achievements have been achieved, the employment of MPcs/O₂ catalytic system in other organic transformations has yet to be developed.

  Scheme 1

  

  Scheme 1.  Metal phthalocyanine compound structure

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  Recently, the groups of Singh^[16] and Piersanti^[17] have presented FePc-catalyzed N-alkylation of heterocyclic amines, synthesis of imines, and C3-benzylation of indoles via either transfer hydrogenation or acceptorless dehydrogenation methodology under inert atmosphere. The groups of Zhang, Xu and Paul have also independently demonstrated Ru₃(CO)₁₂-, Ni(MeTAA)-catalyzed dehydrogenative syntheses of quinazolines under inert atmosphere.^[18] For above transformations, alcohols were utilized as suitable coupling partners with only H₂O and/or H₂ gas generated as the chemical waste, which is more atom-economic and environmentally benign. Very recently, Wang, Xiao and co-workers^[19] have reported acceptorless dehydrogenation and aerobic oxidation of alcohols with binuclear Rh(Ⅱ) complexes, in which reactions under air are generally faster and operationally simpler than under argon.

  Despite the above progress, for the synthesis of quinazoline with 2-aminobenzyl and benzonitrile alcohols, most of these methods require expensive catalysts, toxic reagents, excess oxidants, or harsh conditions, which limits their further applications^{[18, 20]} (Scheme 2). As for quinoline, the groups of Namitharan and Paul^[21] have reported nano- Fe₂O₃-, Cu(Ⅱ)-complex catalyzed syntheses of quinolines under longer time. On the basis of our experience in this area, ^[22] herein we developed MPcs (M＝Fe, Co and Cu) catalyzed doxidative coupling of 2-aminobenzyl alcohols with nitriles to access quinazolines under air.

  Scheme 2

  

  Scheme 2.  Synthesis of quinazoline by various methods

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  2.   Results and discussion

  2-Aminophenylmethanol (1a) (0.5 mmol) and benzonitrile (2a) (0.5 mmol) were utilized as the model substrates to optimize the reaction conditions (Table 1). Initially, various solvents, such as toluene, dioxane, tetrahydrofuran (THF), ^tBuOH, and ^tAmOH, were examined in the presence of Fe(Ⅱ)Pc (5 mol%) and KO^tBu at 100 ℃ for 12 h (Table 1, Entries 1~5). ^tAmOH was found to be the best choice to afford quinazoline 3aa in 59% yield (Table 1, Entry 5). Subsequently, other common strong bases, including KOH, NaO^tBu, NaOH, and CsOH•H₂O, were also texted (Table 1, Entries 6~9). To our delight, product 3aa could be obtained in 63% yield when CsOH•H₂O was utilized (Table 1, Entry 9). Next, we also tried to perform the reaction under Ar, and even we increased temperature to 120 ℃, the yield of 3aa was 16%, which supressed the reaction efficiency tremendously (Table 1, Entries 10, 11). When the temperature was increased to 120 ℃, quinazoline 3aa could be isolated in 83% yield (Table 1, Entry 12). Finally, the effect of other metal catalysts on reaction performance was investigated (Table 1, Entries 13~16). Replacement of Fe(Ⅱ)Pc with FeCl₂, a decreased reactivity was observed. Meanwhile, when other MPcs, such as Co(Ⅱ)Pc and Cu(Ⅱ)Pc, were employed, the desired product 3aa could be isolated in 71% and 60% yields, respectively. In the absence of metal catalyst, 3aa could only be generated in 40% yield.

  Table 1

  

  Table 1.  Optimization of reaction conditions of synthesis of quinazoline^a

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  Entry	Catalyst	Solvent	Base	Yield/%
  1	Fe(Ⅱ)Pc	Toluene	KO'Bu	4
  2	Fe(Ⅱ)Pc	Dioxane	KO'Bu	8
  3	Fe(Ⅱ)Pc	THF	KO'Bu	19
  4	Fe(Ⅱ)Pc	'BuOH	KO'Bu	35
  5	Fe(Ⅱ)Pc	'AmOH	KO'Bu	59
  6	Fe(Ⅱ)Pc	'AmOH	KOH	43
  7	Fe(Ⅱ)Pc	'AmOH	NaO'Bu	42
  8	Fe(Ⅱ)Pc	'AmOH	NaOH	39
  9	Fe(Ⅱ)Pc	'AmOH	CsOH•H2O	63
  10b	Fe(Ⅱ)Pc	'AmOH	CsOH•H2O	16
  11b, c	Fe(Ⅱ)Pc	'AmOH	CsOH•H2O	16
  12c	Fe(Ⅱ)Pc	'AmOH	CsOH•H2O	83
  13c	FeCl2	'AmOH	CsOH•H2O	48
  14c	Co(Ⅱ)Pc	'AmOH	CsOH•H2O	71
  15c	Cu(Ⅱ)Pc	'AmOH	CsOH•H2O	60
  16c	—	'AmOH	CsOH•H2O	40
  a Reaction conditions: 1a (0.5 mmol), 2a (0.5 mmol), metal catalyst (5 mol%), base (0.5 equiv.), solvent (1 mL), 100 ℃, 12 h, under air. Isolated yield. b Ar. c 120 ℃.

  With the optimized conditions in hand (Table 1, Entry 11), the substrate scope of o-hydroxymethyl anilines (1) and nitriles (2) was investigated (Table 2).

  Table 2

  

  Table 2.  Substrate scope of o-hydroxymethyl anilines and nitriles^a

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  Initially, para- and meta-substituted benzonitriles bearing both electron-donating (Me and OMe) and electron- withdrawing (CF₃, Cl and F) groups reacted with (2-aminophenyl) methanol (1a) smoothly to afford the corresponding products 3aa~3ai in 57%~86% yields. For ortho-methyl benzonitrile (2j) and 1-naphthonitrile (2k), products 3aj and3ak were obtained in 44% and 47% yields, respectively, probably due to the steric hindrance effect. When 2-naphthonitrile (2l) was employed, the corresponding product 3al was isolated in 69% yield. Compared with aromatic nitriles, heterocyclic and aliphatic nitriles were less reactive.^[19-21] Gratefully, for thiophene-2-carbonitrile (2m) and isonicotinonitrile (2n), quinazolines 3am and 3an could be obtained in 74% and 69% yields, respectively. Meanwhile, when the reaction was performed at 120 ℃ for 24 h, the aliphatic nitriles were also tolerated to provide 3ao~3as in 49%~74% yields. Moreover, other o-hydroxymethyl anilines were also successfully employed in current protocol, which coupled with aliphatic nitriles to furnish the corresponding products 3bp~3cr in recent yields. To compare the relative reactivity of MPcs, Co(Ⅱ)Pc and Cu(Ⅱ)Pc complexes were also examined. In most cases, Fe(Ⅱ)Pc exhibited higher efficiency, while Cu(Ⅱ)Pc exhibited lower activity.

  Compared with quinazolines, quinolines are also important nitrogen-containing aromatics, which could also be accessed from o-hydroxymethyl anilines. We initiated our investigation by choosing 2-aminophenylmethanol (1a) (0.5 mmol) and acetophenone (4a) (0.5 mmol) as the model substrates (Table 3). To our delight, the desired product 5aa could be isolated in 55% yield in the presence of Fe(Ⅱ)Pc (5 mol%), CsOH•H₂O (0.5 equiv.) in ^tAmOH (1 mL) at 120 ℃ for 12 h (Table 3, Entry 1). Based on our experience in the synthesis of quinazolines, KO^tBu was also examined to give 5aa in 66% yield (Table 3, Entry 2). The reactivity could be further improved when the reaction was performed in toluene, which provided 5aa in 70% yield (Table 3, Entry 3). Similarly, other strong bases were also tested, which all gave inferior results (Table 3, Entries 4~6). Finally, when Co(Ⅱ)Pc and Cu(Ⅱ)Pc were utilized, quinoline 5aa could be isolated in up to 77% yield (Table 3, Entries 7, 8).

  Table 3

  

  Table 3.  Optimization of reaction conditions of synthesis of quinoline^a

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  Entry	Catalyst	Solvent	Base	Yieldb/%
  1	Fe(Ⅱ)Pc	tAmOH	CsOH•H2O	55
  2	Fe(Ⅱ)Pc	tAmOH	KOtBu	66
  3	Fe(Ⅱ)Pc	Toluene	KOtBu	70
  4	Fe(Ⅱ)Pc	Toluene	KOH	65
  5	Fe(Ⅱ)Pc	Toluene	NaOtBu	67
  6	Fe(Ⅱ)Pc	Toluene	NaOH	61
  7	Co(Ⅱ)Pc	Toluene	KOtBu	72
  8	Cu(Ⅱ)Pc	Toluene	KOtBu	77
  a Reaction conditions: 1a (0.5 mmol), 4a (0.5 mmol), MPc's (5 mol%), base (0.5 equiv.), solvent (1 mL), 120 ℃, 12 h, under air. b Isolated yield.

  With the optimized conditions in hand (Table 3, Entry 8), the substrate scope of ketones 4 was explored (Table 4). It was found that para-, meta-, and ortho-substituted ketones 4 were compatible with the catalytic system, which gave the corresponding quinolines 5aa~5ae in 72%~77% yields. Meanwhile, 1-(thiophen-2-yl)ethan-1-one (4f) also reacted with 1a smoothly to afford 5af in 65% yield. Compared with Fe(Ⅱ)Pc and Co(Ⅱ)Pc, Cu(Ⅱ)Pc clearly demonstrated higher reactivity.

  Table 4

  

  Table 4.  Substrate scope of ketones^a

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  To explore the reaction mechanism, a set of control experiments were carried out (Scheme 3). When the reaction between 1a and 2a was interrupted after 10 min, quinazoline 3aa could be isolated in 15% yield accom- panied with generation of aminobenzaldehyde (6) in 8% yield (Scheme 3a). Subsequently, when 1a itself was employed under optimized conditions, intermediate 6 was generated in 10% yield. In the absence of Fe(Ⅱ)Pc, inter-mediate 6 could not be detected, indicating the importance of MPCs in aerobic oxidation of 2-aminobenzyl alcohols (Scheme 3b). Next, when 2a itself was employed under optimized conditions, benzamide 7 was isolated in 92% yield. Without CsOH•H₂O, intermediate 7 could not be detected, indicating the importance of base in hydration of nitriles (Scheme 3c). Finally, condensation between 6 and 7 under optimized conditions delivered product 3aa in 72% yield (Scheme 3d).

  Scheme 3

  

  Scheme 3.  Control experiments

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  On the basis of above discussion and related ref- erences, ^{[14-15a, 23]} a plausible reaction mechanism was proposed (Scheme 4). Initially, autoxidation of MPcs would give μ-oxo-bridged dimetal(Ⅲ) complex Ⅰ, which could further undergo dissociation to form fragments Ⅱ and Ⅲ.^[14] The formation of intermediate Ⅲ could further be confirmed by mass spectrometry (MS) analysis. Intermediate Ⅱ could continue to react with 2-aminophenylmethanol to form intermediate Ⅳ, while intermediate Ⅲ could combine with intermediate Ⅱ to form intermediate Ⅰ. Intermediate Ⅳ rearranged to give the aminobenzaldehyde6 which underwent condensation reaction with benzamide 7 (hydration from nitriles 2) or ketone 4a would ultimately deliver quinazoline 3aa and quinoline 5aa and generated the intermediate Ⅴ through hydrogen atom transfer process.^[23] Finally, the generated intermediate Ⅴ species was reoxidized into the intermediate Ⅰ species by O₂ to complete the catalytic cycle.

  Scheme 4

  

  Scheme 4.  Proposed mechanism

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  3.   Conclusions

  In conclusion, we have successfully disclosed a facile and efficient methodology for MPcs (M＝Fe, Co and Cu) catalyzed syntheses of quinazolines and quinolines from 2-aminobenzyl alcohols and other coupling partners. The current strategy exhibited several unique characteristics, including earth-abundant transition metals, aerobic oxidation, environmental benignity, atom economy, and operational convenience.

  4.   Experimental section

  4.1   General procedure for preparation of quinazo-lines 3

  To an oven-dried 15 mL sealed tube were added 2- aminophenylmethanol (1) (0.5 mmol), benzonitrile (2) (0.5 mmol), CsOH•H₂O (49.89 mg, 0.5 equiv.), and MPcs (5 mol%) [Fe(Ⅱ)Pc (14.21 mg), Co(Ⅱ)Pc (14.29 mg), or Cu(Ⅱ)Pc (14.40 mg)] in ^tAmOH (1 mL) under air atmosphere. The reaction mixture was stirred at 120 ℃ for 12 h and cooled to room temperature afterwards. After removal of organic solvent, the residue was purified by thin-layer chromatography (TLC) on silica gel plates using ethyl acetate (EA)/petroleum ether (PE) as eluent to afford the corresponding quinazolines 3.^[20]

  2-Phenylquinazoline (3aa): Purified using PE/EA (V:V＝15:1) as an eluent (R_f＝0.4); yellow solid; 85.53 mg, 83% yield (catalyzed by Fe(Ⅱ)Pc); 75.22 mg, 73% yield (catalyzed by Co(Ⅱ)Pc); 61.83 mg, 60% yield (catalyzed by Cu(Ⅱ)Pc). m.p. 99~100 ℃; ¹H NMR (400 MHz, CDCl₃) δ: 9.29 (s, 1H), 8.65~8.59 (m, 2H), 7.98 (d, J＝8.0 Hz, 1H), 7.75~7.64 (m, 2H), 7.53~7.43 (m, 3H), 7.38 (t, J＝7.5 Hz, 1H); ¹³C NMR (101 MHz, CDCl₃) δ: 160.9, 160.4, 150.6, 138.1, 134.0, 130.7, 128.7, 128.6, 127.2, 127.1, 123.5.

  2-(4-Methylphenyl)quinazoline (3ab): Purified using PE/EA (V:V＝15:1) as an eluent (R_f＝0.45); yellow solid; 77.03 mg, 70% yield (catalyzed by Fe(Ⅱ)Pc); 74.83 mg, 68% yield (catalyzed by Co(Ⅱ)Pc); 62.73 mg, 57% yield (catalyzed by Cu(Ⅱ)Pc). m.p. 100~101 ℃; ¹H NMR (400 MHz, CDCl₃) δ: 9.41 (s, 1H), 8.51 (d, J＝8.2 Hz, 2H), 8.05 (dd, J＝8.3, 0.8 Hz, 1H), 7.90~7.82 (m, 2H), 7.60~7.50 (m, 1H), 7.33 (d, J＝8.0 Hz, 2H), 2.43 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ: 161.2, 160.5, 150.8, 140.8, 135.3, 134.0, 129.4, 128.5, 127.1, 127.0, 123.5, 21.5.

  2-(4-Methoxyphenyl)quinazoline (3ac): Purified using PE/EA (V:V＝15:1) as an eluent (R_f＝0.42); yellow solid; 72.01 mg, 61% yield (catalyzed by Fe(Ⅱ)Pc); 61.3 mg, 52% yield (catalyzed by Co(Ⅱ)Pc); 67.29 mg, 57% yield (catalyzed by Cu(Ⅱ)Pc). m.p. 84~86 ℃; ¹H NMR (400 MHz, CDCl₃) δ: 9.39 (s, 1H), 8.62~8.50 (m, 2H), 8.05~7.97 (m, 1H), 7.88~7.81 (m, 2H), 7.58~7.49 (m, 1H), 7.06~7.00 (m, 2H), 3.88 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ: 161.8, 160.4, 150.8, 134.0, 130.7, 130.2, 128.9, 128.4, 127.1, 126.7, 123.3, 114.0, 55.4.

  2-(4-(Trifluoromethyl)phenyl)quinazoline (3ad): Purified using PE/EA (V:V＝15:1) as an eluent (R_f＝0.4); yellow solid; 117.85 mg, 86% yield (catalyzed by Fe(Ⅱ)Pc); 104.15 mg, 76% yield (catalyzed by Co(Ⅱ)Pc); 95.93 mg, 70% yield (catalyzed by Cu(Ⅱ)Pc). m.p. 183~184 ℃; ¹H NMR (400 MHz, CDCl₃) δ: 9.45 (s, 1H), 8.72 (d, J＝8.1 Hz, 2H), 8.08 (d, J＝8.9 Hz, 1H), 7.95~7.87 (m, 2H), 7.77 (d, J＝8.3 Hz, 2H), 7.67~7.60 (m, 1H); ¹³C NMR (101 MHz, CDCl₃) δ: 160.6, 159.6, 150.6, 141.3, 134.4, 132.1 (J_C-F＝32.3 Hz), 128.8, 128.8, 127.9, 127.2, 125.5 (J_C-F＝3.7 Hz), 123.8, 122.9. ¹⁹F NMR (376 MHz, CDCl₃) δ: －62.66.

  2-(4-Chlorophenyl)quinazoline (3ae): Purified using PE/EA (V:V＝15:1) as an eluent (R_f＝0.37); yellow solid; 80.41 mg, 67% yield (catalyzed by Fe(Ⅱ)Pc); 68.41 mg, 57% yield (catalyzed by Co(Ⅱ)Pc); 70.81 mg, 59% yield (catalyzed by Cu(Ⅱ)Pc). m.p. 129~131 ℃; ¹H NMR (400 MHz, CDCl₃) δ: 9.43 (s, 1H), 8.60~8.53 (m, 2H), 8.06 (d, J＝8.0 Hz, 1H), 7.94~7.86 (m, 2H), 7.61 (td, J＝7.4, 1.0 Hz, 1H), 7.52~7.44 (m, 2H); ¹³C NMR (101 MHz, CDCl₃) δ: 160.5, 160.1, 150.7, 136.8, 136.5, 134.2, 129.9, 128.8, 128.6, 127.4, 127.1, 123.6.

  2-(4-Iodophenyl)quinazoline (3af): Purified using PE/EA (V:V＝15:1) as an eluent as an eluent (R_f＝0.34); yellow solid; 94.61 mg, 57% yield (catalyzed by Fe(Ⅱ)Pc); 92.95 mg, 56% yield (catalyzed by Co(Ⅱ)Pc); 74.69 mg, 45% yield (catalyzed by Cu(Ⅱ)Pc). m.p. 126~127 ℃; ¹H NMR (400 MHz, CDCl₃) δ: 9.40 (s, 1H), 8.36~8.29 (m, 2H), 8.04 (d, J＝8.8 Hz, 1H), 7.92~7.80 (m, 4H), 7.63~7.55 (m, 1H); ¹³C NMR (101 MHz, CDCl₃) δ: 160.5, 160.2, 150.65, 137.8, 137.6, 134.3, 130.3, 128.7, 127.5, 127.2, 123.7, 97.8.

  2-(m-Tolyl)quinazoline (3ag): Purified using PE/EA (V:V＝15:1) as an eluent (R_f＝0.54); yellow solid; 84.74 mg, 77% yield(catalyzed by Fe(Ⅱ)Pc); 71.53 mg, 65% yield (catalyzed by Co(Ⅱ)Pc); 66.03 mg, 60% yield (catalyzed by Cu(Ⅱ)Pc). m.p. 94~95 ℃; ¹H NMR (400 MHz, CDCl₃) δ: 9.43 (s, 1H), 8.42 (d, J＝5.8 Hz, 2H), 8.07 (d, J＝9.0 Hz, 1H), 7.91~7.84 (m, 2H), 7.57 (td, J＝7.4, 0.9 Hz, 1H), 7.42 (t, J＝7.4 Hz, 1H), 7.31 (d, J＝7.5 Hz, 1H), 2.48 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ: 161.2, 160.4, 150.7, 138.2, 138.0, 134.0, 131.4, 129.1, 128.6, 127.2, 127.1, 125.8, 123.5, 21.6.

  2-(3-Fluorophenyl)quinazoline (3ah): Purified using PE/EA (V:V＝15:1) as an eluent (R_f＝0.35); yellow solid, 72.82 mg, 65% yield (catalyzed by Fe(Ⅱ)Pc); 77.3 mg, 69% yield (catalyzed by Co(Ⅱ)Pc); 68.34 mg, 61% yield (catalyzed by Cu(Ⅱ)Pc). m.p. 92~93 ℃; ¹H NMR (400 MHz, CDCl₃) δ: 9.42 (s, 1H), 8.45~8.36 (m, 1H), 8.36~8.29 (m, 1H), 8.06 (d, J＝8.0 Hz, 1H), 7.92~7.84 (m, 2H), 7.60 (t, J＝7.5, 8.0 Hz, 1H), 7.53~7.42 (m, 1H), 7.22~7.14 (m, 1H); ¹³C NMR (101 MHz, CDCl₃) δ: 163.3 (J_C-F＝244.8 Hz), 160.5, 159.8 (J_C-F＝3.2 Hz), 150.6, 140.5 (J_C-F＝7.9 Hz), 134.3, 130.1 (J_C-F＝8.0 Hz), 128.7, 127.6, 127.1, 124.2 (J_C-F＝2.8 Hz), 123.8, 117.5 (J_C-F＝21.4 Hz), 115.4 (J_C-F＝23.3 Hz). ¹⁹F NMR (376 MHz, CDCl₃) δ: -113.20.

  2-(3-Methoxyphenyl)quinazoline (3ai): Purified using PE/EA (V:V＝15:1) as an eluent (R_f＝0.26); yellow solid; 79.09 mg, 67% yield (catalyzed by Fe(Ⅱ)Pc); 59.02 mg, 50% yield (catalyzed by Co(Ⅱ)Pc); 55.48 mg, 47% yield (catalyzed by Cu(Ⅱ)Pc). m.p. 71~72℃; ¹H NMR (400 MHz, CDCl₃) δ: 9.50 (s, 1H), 8.10 (d, J＝8.5 Hz, 1H), 7.99~7.88 (m, 3H), 7.71~7.63 (m, 1H), 7.42~7.30 (m, 3H), 2.61 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ: 160.7, 160.4, 160.1, 150.6, 139.6, 134.0, 129.7, 128.6, 127.3, 127.09, 123.6, 121.2, 117.2, 113.2, 55.4.

  2-(o-Tolyl)quinazoline (3aj): Purified using PE/EA (V:V＝15:1) as an eluent (R_f＝0.36); yellow oil; 48.42 mg, 44% yield (catalyzed by Fe(Ⅱ)Pc); 58.32 mg, 53% yield (catalyzed by Co(Ⅱ)Pc); 45.12 mg, 41% yield (catalyzed by Cu(Ⅱ)Pc). ¹H NMR (400 MHz, CDCl₃) δ: 9.50 (s, 1H), 8.10 (d, J＝8.5 Hz, 1H), 7.99~7.88 (m, 3H), 7.71~7.63 (m, 1H), 7.42~7.30 (m, 3H), 2.61 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ: 164.1, 160.1, 150.4, 138.6, 137.4, 134.1, 131.3, 130.7, 129.3, 128.6, 127.6, 127.1, 126.0, 122.9, 21.1.

  2-(Naphthalen-1-yl)quinazoline (3ak): Purified using PE/EA (V:V＝15:1) as an eluent (R_f＝0.36); yellow solid; 60.18 mg, 47% yield (catalyzed by Fe(Ⅱ)Pc); 57.62 mg, 45% yield (catalyzed by Co(Ⅱ)Pc); 60.18 mg, 47% yield (catalyzed by Cu(Ⅱ)Pc). m.p. 118~121 ℃; ¹H NMR (400 MHz, CDCl₃) δ: 9.57 (s, 1H), 8.71 (d, J＝9.2 Hz, 1H), 8.20~8.13 (m, 2H), 8.02~7.88 (m, 4H), 7.71~7.59 (m, 2H), 7.58~7.48 (m, 2H); ¹³C NMR (101 MHz, CDCl₃) δ: 163.5, 160.5, 150.6, 136.4, 134.4, 134.3, 131.3, 130.4, 129.7, 128.7, 128.6, 127.8, 127.2, 126.9, 126.0, 126.0, 125.4, 123.2.

  2-(Naphthalen-2-yl)quinazoline (3al): Purified using PE/EA (V:V＝15:1) as an eluent (R_f＝0.4); yellow solid; 88.35 mg, 69% yield (catalyzed by Fe(Ⅱ)Pc); 83.23 mg, 65% yield (catalyzed by Co(Ⅱ)Pc); 75.55 mg, 59% yield (catalyzed by Cu(Ⅱ)Pc). m.p. 132~134 ℃; ¹H NMR (400 MHz, CDCl₃) δ: 9.52 (s, 1H), 9.17 (s, 1H), 8.74 (dd, J＝8.6, 1.7 Hz, 1H), 8.14 (dd, J＝8.4, 0.7 Hz, 1H), 8.08~7.87 (m, 5H), 7.63 (td, J＝5.8, 1.2 Hz, 1H), 7.59~7.49 (m, 2H); ¹³C NMR (101 MHz, CDCl₃) δ: 161.0, 160.5, 150.8, 135.5, 134.8, 134.1, 133.5, 129.4, 129.0, 128.6, 128.3, 127.8, 127.3, 127.2, 126.3, 125.5, 123.6.

  2-(Thiophen-2-yl)quinazoline (3am): Purified using PE/EA (V:V＝15:1) as an eluent (R_f＝0.35); yellow solid; 78.45 mg, 74% yield (catalyzed by Fe(Ⅱ)Pc); 66.79 mg, 63% yield (catalyzed by Co(Ⅱ)Pc); 65.73 mg, 62% yield (catalyzed by Cu(Ⅱ)Pc). m.p. 131~132 ℃; ¹H NMR (400 MHz, CDCl₃) δ: 9.34 (s, 1H), 8.15 (dd, J＝3.7, 1.2 Hz, 1H), 8.00 (d, J＝8.9 Hz, 1H), 7.89~7.82 (m, 2H), 7.58~7.49 (m, 2H), 7.19 (m, 1H); ¹³C NMR (101 MHz, CDCl₃) δ: 160.6, 157.9, 150.6, 143.9, 134.4, 123.0, 129.3, 128.4, 128.2, 127.3, 127.0, 123.4.

  2-(Pyridin-4-yl)quinazoline (3an): Purified using PE/ EA (V:V＝15:1) as an eluent (R_f＝0.4); yellow solid; 68.39 mg, 66% yield (catalyzed by Fe(Ⅱ)Pc); 62.17 mg, 60% yield (catalyzed by Co(Ⅱ)Pc); 64.24 mg, 62% yield (catalyzed by Cu(Ⅱ)Pc). m.p. 123~124 ℃; ¹H NMR (400 MHz, CDCl₃) δ: 9.47 (s, 1H), 8.80 (dd, J＝4.6, 1.5 Hz, 2H), 8.44 (dd, J＝4.5, 1.6 Hz, 2H), 8.10 (d, J＝8.9 Hz, 1H), 7.98~7.89 (m, 2H), 7.66 (td, J＝8.0, 1.0 Hz, 1H); ¹³C NMR (101 MHz, CDCl₃) δ: 160.7, 158.9, 150.5, 150.5, 145.3, 134.5, 128.9, 128.3, 127.2, 124.1, 122.3.

  2-n-Butylquinazoline (3ao): Purified using PE/EA (V:V＝15:1) as an eluent (R_f＝0.34);yellow oil; 45.59 mg, 49% yield (catalyzed by Fe(Ⅱ)Pc); 42.81 mg, 46% yield (catalyzed by Co(Ⅱ)Pc); 41.88 mg, 45% yield (catalyzed by Cu(Ⅱ)Pc). ¹H NMR (400 MHz, CDCl₃) δ: 9.34 (s, 1H), 7.98 (d, J＝9.0 Hz, 1H), 7.90~7.84 (m, 2H), 7.63~7.53 (m, 1H), 3.13 (t, J＝7.7 Hz, 2H), 1.98~1.86 (m, 2H), 1.53~1.39 (m, 2H), 0.98 (t, J＝7.4 Hz, 3H). ¹³C NMR (101 MHz, CDCl₃) δ: 167.9, 160.3, 150.3, 133.9, 127.8, 127.0, 126.8, 123.0, 39.7, 31.1, 22.6, 13.9.

  2-iso-Butylquinazoline (3ap): Purified using PE/EA (V:V＝15:1) as an eluent (R_f＝0.35); yellow oil; 68.86 mg, 74% yield (catalyzed by Fe(Ⅱ)Pc); 58.63 mg, 63% yield (catalyzed by Co(Ⅱ)Pc); 53.04 mg, 57% yield (catalyzed by Cu(Ⅱ)Pc). ¹H NMR (400 MHz, CDCl₃) δ: 9.35 (s, 1H), 7.99 (d, 1H), 7.88 (t, J＝7.8 Hz, 2H), 7.59 (t, J＝7.5 Hz, 1H), 3.01 (d, J＝7.3 Hz, 2H), 2.45~2.37 (m, 1H), 1.01 (d, J＝6.7 Hz, 6H); ¹³C NMR (101 MHz, CDCl₃) δ: 167.2, 160.3, 150.3, 134.0, 128.0, 127.1, 126.9, 123.0, 77.4, 77.1, 76.8, 48.9, 28.8, 22.6.

  2-tert-Butylquinazoline (3aq): Purified using PE/EA (V:V＝15:1) as an eluent (R_f＝0.35); yellow oil; 67.93 mg, 73% yield (catalyzed by Fe(Ⅱ)Pc); 55.83 mg, 60% yield (catalyzed by Co(Ⅱ)Pc); 60.49 mg, 65% yield (catalyzed by Cu(Ⅱ)Pc). ¹H NMR (400 MHz, CDCl₃) δ: 9.36 (s, 1H), 8.00 (d, J＝8.3 Hz, 1H), 7.89~7.80 (m, 2H), 7.61~7.52 (m, 1H), 1.52 (s, 9H); ¹³C NMR (101 MHz, CDCl₃) δ: 173.5, 159.9, 150.2, 133.6, 128.4, 126.9, 126.8, 122.9, 39.6, 29.7, 13.7.

  2-Cyclopropylquinazoline (3ar): Purified using PE/EA (V:V＝15:1) as an eluent (R_f＝0.35); yellow oil; 56.13 mg, 66% yield (catalyzed by Fe(Ⅱ)Pc); 48.47 mg, 57% yield (catalyzed by Co(Ⅱ)Pc); 52.73 mg, 62% yield (catalyzed by Cu(Ⅱ)Pc). ¹H NMR (400 MHz, CDCl₃) δ: 9.22 (s, 1H), 7.90 (d, J＝8.2 Hz, 1H), 7.86~7.77 (m, 2H), 7.54~7.47 (m, 1H), 2.45~2.35 (m, 1H), 1.30~1.24 (m, 2H), 1.16~1.10 (m, 2H); ¹³C NMR (101 MHz, CDCl₃) δ: 168.4, 160.3, 150.3, 133.9, 127.5, 127.1, 126.3, 123.2, 18.6, 10.6.

  2-Cyclohexanylquinazoline (3as): Purified using PE/ EA (V:V＝15:1) as an eluent (R_f＝0.35); yellow oil; 60.46 mg, 57% yield (catalyzed by Fe(Ⅱ)Pc); 48.79 mg, 46% yield (catalyzed by Co(Ⅱ)Pc); 44.55 mg, 42% yield (catalyzed by Cu(Ⅱ)Pc). ¹H NMR (400 MHz, CDCl₃) δ: 9.35 (s, 1H), 7.98 (d, J＝8.9 Hz, 1H), 7.86 (t, J＝7.5 Hz, 2H), 7.57 (t, J＝8.0 Hz, 1H), 3.19~2.94 (m, 1H), 2.13~2.05 (m, 2H), 1.95~1.85 (m, 2H), 1.84~1.72 (m, 3H), 1.53~1.18 (m, 4H); ¹³C NMR (101 MHz, CDCl₃) δ: 168.3, 160.3, 150.3, 133.9, 127.5, 127.1, 126.2, 123.2, 18.6, 10.6.

  2-(2-iso-Butyl)-8-methylquinazoline (3bp): Purified using PE/EA (V:V＝15:1) as an eluent (R_f＝0.48); yellow oil; 56.04 mg, 56% yield (catalyzed by Fe(Ⅱ)Pc); 53.03 mg, 53% yield (catalyzed by Co(Ⅱ)Pc); 54.04 mg, 54% yield (catalyzed by Cu(Ⅱ)Pc). ¹H NMR (400 MHz, CDCl₃) δ: 9.27 (s, 1H), 7.68 (d, J＝7.5 Hz, 2H), 7.44 (t, J＝7.6 Hz, 1H), 3.02 (d, J＝7.2 Hz, 2H), 2.75 (s, 3H), 2.49~2.32 (m, 1H), 1.02 (d, J＝6.7 Hz, 6H); ¹³C NMR (101 MHz, CDCl₃) δ: 166.1, 160.1, 149.5, 136.5, 133.6, 126.4, 124.7, 122.9, 48.8, 28.4, 22.6, 17.0.

  2-(2-tert-Butyl)-8-methylquinazoline (3bq): Purified using PE/EA (V:V＝15:1) as an eluent (R_f＝0.35); yellow oil; 63.04 mg, 63% yield (catalyzed by Fe(Ⅱ)Pc); 63.04 mg, 58% yield (catalyzed by Co(Ⅱ)Pc); 51.03 mg, 51% yield (catalyzed by Cu(Ⅱ)Pc). ¹H NMR (400 MHz, CDCl₃) δ: 9.30 (s, 1H), 7.67 (dd, J＝4.6, 3.7 Hz, 2H), 7.42 (t, J＝7.6 Hz, 1H), 2.75 (s, 3H), 1.53 (s, 10H); ¹³C NMR (101 MHz, CDCl₃) δ: 172.4, 160.0, 149.0, 136.9, 133.3, 126.4, 124.5, 122.7, 39.7, 29.7, 16.8.

  2-(2-iso-Butyl)-6-methylquinazoline (3cp): Purified using PE/EA (V:V＝15:1) as an eluent (R_f＝0.35); yellow oil; 48.03 mg, 48% yield (catalyzed by Fe(Ⅱ)Pc); 50.03 mg, 50% yield (catalyzed by Co(Ⅱ)Pc); 40.03 mg, 40% yield (catalyzed by Cu(Ⅱ)Pc). ¹H NMR (400 MHz, CDCl₃) δ: 9.26 (s, 1H), 7.88 (d, J＝8.6 Hz, 1H), 7.70 (dd, J＝8.7, 1.7 Hz, 1H), 7.63 (s, 1H), 2.98 (d, J＝7.3 Hz, 2H), 2.54 (s, 3H), 2.43~2.34 (m, 1H), 1.00 (d, J＝6.7 Hz, 6H); ¹³C NMR (101 MHz, CDCl₃) δ: 166.4, 159.5, 148.9, 137.0, 136.2, 127.6, 125.7, 123.0, 48.8, 28.8, 22.5, 21.5.

  2-(2-tert-Butyl)-6-methylquinazoline (3cq): Purified using PE/EA (V:V＝15:1) as an eluent (R_f＝0.35); yellow oil; 60.04 mg, 60% yield (catalyzed by Fe(Ⅱ)Pc); 53.03 mg, 53% yield (catalyzed by Co(Ⅱ)Pc); 43.03 mg, 43% yield (catalyzed by Cu(Ⅱ)Pc). ¹H NMR (400 MHz, CDCl₃) δ: 9.27 (s, 1H), 7.89 (d, J＝8.6 Hz, 1H), 7.73~7.65 (m, 1H), 7.64~7.59 (m, 1H), 2.54 (s, 3H), 1.51 (s, 9H); ¹³C NMR (101 MHz, CDCl₃) δ: 172.8, 159.3, 148.8, 136.8, 135.9, 128.0, 125.6, 122.8, 39.4, 29.7, 21.6.

  2-(2-Cyclopropyl)-6-methylquinazoline (3cr): Purified using PE/EA (V:V＝15:1) as an eluent (R_f＝0.45); yellow oil; 53.38 mg, 58% yield (catalyzed by Fe(Ⅱ)Pc); 49.71 mg, 54% yield (catalyzed by Co(Ⅱ)Pc); 44.18 mg, 48% yield (catalyzed by Cu(Ⅱ)Pc). ¹H NMR (400 MHz, CDCl₃) δ: 9.15 (s, 1H), 7.80 (d, J＝8.6 Hz, 1H), 7.67 (dd, J＝8.6, 1.6 Hz, 1H), 7.60 (s, 1H), 2.53 (s, 3H), 2.41~2.33 (m, 1H), 1.28~1.22 (m, 2H), 1.16~1.09 (m, 2H); ¹³C NMR (101 MHz, CDCl₃) δ: 167.6, 159.7, 149.0 136.3, 136.3, 127.2, 125.8, 123.2, 21.5, 18.5, 10.4.

  4.2   General procedure for the preparation of quinolines 5

  To an oven-dried 15 mL sealed tube were added 2-aminophenylmethanol (1) (0.5 mmol), acetophenone (4) (0.5 mmol), KO^tBu (28.03 mg, 0.5 equiv.), and MPcs (5 mol%) [Fe(Ⅱ)Pc (14.21 mg), Co(Ⅱ)Pc (14.29 mg), or Cu(Ⅱ)Pc (14.40 mg)] in toluene (1 mL) under air atmosphere. The reaction mixture was stirred at 120 ℃ for 12 h and cooled to room temperature afterwards. After removal of organic solvent, the residue was purified by TLC on silica gel plates using EA/PE as eluent to afford the corresponding quinolines 5.^[21]

  2-Phenylquinline (5aa): Purified using PE/EA (V:V＝15:1) as an eluent (R_f＝0.5); wihte solid; 71.78 mg, 70% yield (catalyzed by Fe(Ⅱ)Pc); 76.91 mg, 75% yield (catalyzed by Co(Ⅱ)Pc); 78.96 mg, 77% yield (catalyzed by Cu(Ⅱ)Pc). m.p. 83~84 ℃; ¹H NMR (400 MHz, CDCl₃) δ: 8.22~8.13 (m, 4H), 7.86 (d, J＝8.6 Hz, 1H), 7.81 (dd, J＝8.1, 1.2 Hz, 1H), 7.76~7.67 (m, 1H), 7.57~7.49 (m, 3H), 7.48~7.42 (m, 1H); ¹³C NMR (101 MHz, CDCl₃) δ: 157.3, 148.4, 139.7, 136.8, 129.9, 129.8, 129.5, 129.0, 127.7, 127.6, 127.3, 126.4, 119.0.

  2-(4-Methylphenyl)quinoline (5ab): Purified using PE/EA (V:V＝15:1) as an eluent (R_f＝0.44); white solid; 73.40 mg, 67% yield (catalyzed by Fe(Ⅱ)Pc); 75.59 mg, 69% yield (catalyzed by Co(Ⅱ)Pc); 85.45 mg, 78% yield (catalyzed by Cu(Ⅱ)Pc). m.p. 82~83 ℃; ¹H NMR (400 MHz, CDCl₃) δ: 8.15 (d, J＝8.5 Hz, 1H), 8.01 (dd, J＝12.1, 8.4 Hz, 3H), 7.72~7.59 (m, 3H), 7.45~7.35 (m, 1H), 7.25 (d, J＝8.0 Hz, 2H), 2.35 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ: 157.3, 148.4, 139.4, 136.9, 136.7, 129.8, 129.7, 129.4, 127.6, 127.2, 126.4, 126.1, 118.8, 21.5.

  2-(4-Chlorphenyl)quinoline (5ac): Purified using PE/EA (V:V＝15:1) as an eluent (R_f＝0.43); white solid; 75.30 mg, 63% yield (catalyzed by Fe(Ⅱ)Pc); 75.28 mg, 63% yield (catalyzed by Co(Ⅱ)Pc); 87.25 mg, 73% yield (catalyzed by Cu(Ⅱ)Pc). m.p. 111~112 ℃; ¹H NMR (400 MHz, CDCl₃) δ: 8.13 (dd, J＝8.4, 1.9 Hz, 2H), 8.10~8.05 (m, 2H), 7.75 (t, J＝7.3 Hz, 2H), 7.73~7.67 (m, 1H), 7.52~7.41 (m, 3H); ¹³C NMR (101 MHz, CDCl₃) δ: 156.0, 148.3, 138.1, 137.0, 135.6, 129.9, 129.7, 129.0, 128.8, 127.5, 127.2, 126.5, 118.5.

  2-(3-Methylphenyl)quinoline (5ad): Purified using PE/EA (V:V＝15:1) as an eluent (R_f＝0.55); yellow oil; 79.97 mg, 73% yield (catalyzed by Fe(Ⅱ)Pc); 83.26 mg, 76% yield (catalyzed by Co(Ⅱ)Pc); 84.36 mg, 77% yield (catalyzed by Cu(Ⅱ)Pc); ¹H NMR (400 MHz, CDCl₃) δ: 8.17 (d, J＝8.5 Hz, 1H), 8.09 (d, J＝8.6 Hz, 1H), 7.99 (s, 1H), 7.89 (d, J＝7.7 Hz, 1H), 7.76 (dd, J＝17.9, 8.3 Hz, 2H), 7.71~7.64 (m, 1H), 7.50~7.42 (m, 1H), 7.37 (t, J＝7.6 Hz, 1H), 7.24 (d, J＝7.5 Hz, 1H), 2.44 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ: 157.6, 148.3, 139.7, 138.5, 136.7, 130.2, 129.8, 129.7, 128.8, 128.3, 127.5, 127.2, 126.3, 124.8, 119.2, 21.7.

  2-(2-Methylphenyl)quinoline (5ae): Purified using PE/EA (V:V＝15:1) as an eluent (R_f＝0.45); white solid; 70.11 mg, 64% yield (catalyzed by Fe(Ⅱ)Pc); 81.07 mg, 74% yield (catalyzed by Co(Ⅱ)Pc); 78.88 mg, 72% yield (catalyzed by Cu(Ⅱ)Pc). m.p. 74~75 ℃; ¹H NMR (400 MHz, CDCl₃) δ: 8.17 (t, J＝6.6 Hz, 2H), 7.84 (dd, J＝8.1, 0.9 Hz, 1H), 7.76~7.69 (m, 1H), 7.57~7.47 (m, 3H), 7.37~7.28 (m, 3H), 2.41 (s, 3H); ¹³C NMR (101 MHz, CDCl₃) δ: 160.3, 148.0, 140.8, 136.1, 136.0, 130.9, 129.8, 129.7, 129.6, 128.5, 127.5, 126.8, 126.4, 126.1, 122.4, 20.4.

  2-(Thiophen-2-yl)quinoline (5af): Purified using PE/EA (V:V＝15:1) as an eluent (R_f＝0.50); white solid; 62.26 mg, 59% yield (catalyzed by Fe(Ⅱ)Pc); 54.87 mg, 52% yield (catalyzed by Co(Ⅱ)Pc); 68.59 mg, 65% yield (catalyzed by Cu(Ⅱ)Pc). m.p. 132~133 ℃; ¹H NMR (400 MHz, CDCl₃) δ: 8.08 (dd, J＝8.4, 4.6 Hz, 1H), 7.75 (t, J＝8.7 Hz, 1H), 7.72~7.65 (m, 1H), 7.49~7.42 (m, 1H), 7.14 (dd, J＝5.0, 3.7 Hz, 1H); ¹³C NMR (101 MHz, CDCl₃) δ: 152.4, 148.1, 145.4, 136.6, 129.8, 129.3, 128.6, 128.1, 127.5, 127.2, 126.1, 125.9, 117.7.

  4.3   Hydrogenation of styrene by evolved hydrogen

  In a typical experimental setup two high pressure tubes were connected using a rubber tube. Under argon atmosphere, the first tube was charged with 2-aminophenyl- methanol (1) (0.5 mmol), benzonitrile (2) (0.5 mmol), CsOH•H₂O (49.89 mg, 0.5 equiv.) and Fe(Ⅱ)Pc (14.21 mg, 5 mol%) in ^tAmOH (1 mL). In the second tube styrene (52.075 mg, 0.5 mmol) and Pd/C (0.1 g) were placed in THF (1 mL) with a magnetic stir bar. Then tubes were placed in oil bath preheated at 120 ℃ for 12 h. The conversion of styrene to ethylbenzene was confirmed by TLC analysis of the reaction mixture present in the second tube containing styrene.

  Supporting Information There are ¹H NMR and ¹³C NMR original spectra of the target compounds. The Supporting Information is available free of charge via the Internet at http://sioc-journal.cn/.

  
  
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• 

  Scheme 1  Metal phthalocyanine compound structure

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  Scheme 2  Synthesis of quinazoline by various methods

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  Scheme 3  Control experiments

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  Scheme 4  Proposed mechanism

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  Table 1.  Optimization of reaction conditions of synthesis of quinazoline^a

  Entry	Catalyst	Solvent	Base	Yield/%
  1	Fe(Ⅱ)Pc	Toluene	KO'Bu	4
  2	Fe(Ⅱ)Pc	Dioxane	KO'Bu	8
  3	Fe(Ⅱ)Pc	THF	KO'Bu	19
  4	Fe(Ⅱ)Pc	'BuOH	KO'Bu	35
  5	Fe(Ⅱ)Pc	'AmOH	KO'Bu	59
  6	Fe(Ⅱ)Pc	'AmOH	KOH	43
  7	Fe(Ⅱ)Pc	'AmOH	NaO'Bu	42
  8	Fe(Ⅱ)Pc	'AmOH	NaOH	39
  9	Fe(Ⅱ)Pc	'AmOH	CsOH•H2O	63
  10b	Fe(Ⅱ)Pc	'AmOH	CsOH•H2O	16
  11b, c	Fe(Ⅱ)Pc	'AmOH	CsOH•H2O	16
  12c	Fe(Ⅱ)Pc	'AmOH	CsOH•H2O	83
  13c	FeCl2	'AmOH	CsOH•H2O	48
  14c	Co(Ⅱ)Pc	'AmOH	CsOH•H2O	71
  15c	Cu(Ⅱ)Pc	'AmOH	CsOH•H2O	60
  16c	—	'AmOH	CsOH•H2O	40
  a Reaction conditions: 1a (0.5 mmol), 2a (0.5 mmol), metal catalyst (5 mol%), base (0.5 equiv.), solvent (1 mL), 100 ℃, 12 h, under air. Isolated yield. b Ar. c 120 ℃.

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  Table 2.  Substrate scope of o-hydroxymethyl anilines and nitriles^a

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  Table 3.  Optimization of reaction conditions of synthesis of quinoline^a

  Entry	Catalyst	Solvent	Base	Yieldb/%
  1	Fe(Ⅱ)Pc	tAmOH	CsOH•H2O	55
  2	Fe(Ⅱ)Pc	tAmOH	KOtBu	66
  3	Fe(Ⅱ)Pc	Toluene	KOtBu	70
  4	Fe(Ⅱ)Pc	Toluene	KOH	65
  5	Fe(Ⅱ)Pc	Toluene	NaOtBu	67
  6	Fe(Ⅱ)Pc	Toluene	NaOH	61
  7	Co(Ⅱ)Pc	Toluene	KOtBu	72
  8	Cu(Ⅱ)Pc	Toluene	KOtBu	77
  a Reaction conditions: 1a (0.5 mmol), 4a (0.5 mmol), MPc's (5 mol%), base (0.5 equiv.), solvent (1 mL), 120 ℃, 12 h, under air. b Isolated yield.

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  Table 4.  Substrate scope of ketones^a

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•