Skip to main content
Download PDF
Download ePub

Cu-catalyzed, Mn-mediated propargylation and allenylation of aldehydes with propargyl bromides

BMC Chemistry volume 16, Article number: 14 (2022) Cite this article

Abstract

A simple, practical, and high chemo-selective method for the synthesis of propargyl alcohol and allenyl alcohols via Cu-catalyzed, Mn-mediated propargylation and allenylation of aldehydes with propargyl bromides has been established. When 3-bromo-1-propyne was conducted under the standard condition, the aldehydes were transformed to the corresponding propargylation products completely, while when 1-bromo-2-pentyne was used, allenic alcohol was the only product. Variety of homopropargyl alcohols and allenyl alcohols were obtained in high yields and the reaction is compatible with broad substrate scopes. In addition, the large-scale reaction could also be proceeded smoothly indicating the potential synthetic applications of this transformation.

Graphical Abstract

Peer Review reports

Introduction

Propargyl and allenyl groups are not only valuable building blocks for further manipulations and organic transformations in organic synthesis [1,2,3,4,5,6,7], but also sever as active structural moieties in plentiful functional molecules which are important in bioactive molecules, pharmaceuticals agents and natural products [8,9,10,11,12,13]. Thus, this interesting and promising synthetic method has been attracting a great deal of attentions [14,15,16,17,18,19,20,21,22,23]. Numerous methods have been established by using propargyl halides and metals to produce the nucleophilic character of the propargyl metal species [24,25,26]. When the nucleophilic receptor is an aldehyde, the homopropargyl alcohol can be obtained by the nucleophilic addition of propargyl metal species and aldehyde [27, 28]. Variety of metals, including In [29,30,31], Sb [32], Pb [33], Ti [34], Cr [35], Ga [36], Sn [37], Zn [38, 39], Mn [40] and Sc [41], have been used for this coupling reaction which could afford the corresponding homopropargyl alcohols. While, the by-product allenyl alcohol is inevitable, which can be owned to the rearrangement of the crucial intermediate progargyl metal species to allenyl metal species [42]. Therefore, a mixture of homopropargyl alcohol and allenyl alcohol were generally obtained. Despite the encouraging progress has been made [43,44,45], long reaction time–cost, moderate yields and low chemo-selectivity has limited the applications. Therefore, there is still demands for the improved method with respect to selectivities for homopropargyl alcohol and allenyl alcohols.

As we known, Cu catalyst, is not only abundant, easy to utilize, and relatively insensitive to water and air, but also has advantageous for the controllable access to Cu(0), Cu(I), Cu(II), and Cu(III) oxidation states [46, 47]; possibly because of its single-electron transfer (SET) and two-electron processes (TEPs) pathway [48, 49]; which make the catalytic system with high catalytic activities and rate. Moreover, Manganese has been widely used in organic reactions by virtue of its environmentally benign and sustainable nature, low cost and versatile reactivity [50, 51]. Up to now, there were only few examples had been reported, but they showed the activity of Mn in the proparylation reaction. So will the combination of Cu-catalyst and Mn powder increase the catalytic efficiency in the proparylation of propargyl bromide with aldehyde?

In this paper, we developed the first example of Cu-catalyzed and Mn-mediated propargylation and allenylation of aldehydes with propargyl bromides under a novel catalytic system, which is covered with advantages of high efficiency, good chemo-selectivity, and wide substrates scopes under mild reaction conditions (Fig. 1).

Fig. 1
figure 1

Previous studies and our concept

Full size image

We initiated our investigation using benzaldehyde (1a) and propargyl bromide (2a) as model substrates which catalyzed by copper salts and Mn powder (Table 1). Without Mn, only trace amount of desired product was observed which indicated that Mn powder is indispensable (Table 1, entry 1). While in the absence of CuBr2, 16% of 3a was produced which demonstrated the great importance of Cu catalyst (entry 2). Screening of different solvents illustrated that MeCN is the best reaction medium, giving the desired product 3a in 47% yield (entry 3). While, only trace amount of product was observed in THF or DCM and 24% in EtOH (entries 4–6). The yield of products dropped sharply when the reaction was carried out in the open system (entry 7). Meanwhile, without the addition of CF3COOH, only 13% yield of 3a was achieved (entry 8). Subsequently, extensive experiments were conducted to investigate the effects of different copper salts on the reaction. Series of Cu catalysts, including CuSO4, CuCl, CuCl2, CuBr and CuI were tested and CuCl gave the best result (entries 9–13). Adding 5 equiv. Mn powder, a remarkable increase has been presented (entry 14). Simultaneously, a light increase of yield was observed by increasing the amount of catalyst (entry 15). Further studies indicated that extending the reaction time to 24 h, 1a can be transformed to 3a completely under the standard conditions (entry 16).

Table 1 The effect of different parameters on the reaction of 1a and 2a.a
Full size table
Table 2 Cu-catalyzed and Mn-mediated propargylation of different aldehydesa
Full size table
Table 3 Cu-catalyzed and Mn-mediated allenylation of different aldehydesa
Full size table

With the optimized setup in hand, we next explored the substrates scope of aldehydes with different functional groups as shown in Table 2. It is pleasing that substrates bearing both electron-donating groups (EDGs) and electron-withdrawing groups (EWGs) can proceed smoothly. For example, substrates 3c, 3e, 3f, 3g, 3h, 3i, 3k and 3o with alkyl and alkoxy groups can be transformed to the corresponding products in excellent yield. Substrates containing the halogen (3b, 3d, 3i, 3j) can also deliver the corresponding products with excellent yields. In addition, disubstituted benzaldehydes, such as 2,4-dimethyl (3m), 2,3-dimethyl (3p), 2,5-difluoro (3n), 2,3-difluoro (3o), 2-methoxy-4-methyl (3q) 3-chloro-5-fluoro (3r), 3-methoxy-4-fluoro (3s) and 3-methyl-4-fluor (3t) benzaldehydes were found to be compatible with the reaction in 85%- 95% yields. To further expand the scopes of the present catalytic system, reactions of heteroaromatic aldehydes including thiophenecarboxaldehyde (3v), pyridylaldehydes (3w and 3x) and quinolinecarboxaldehyde (3y) which contain aromatic heterocycle in the molecules were also explored. Interesting, all of these substrates were compatible with the reaction conditions and produced the homopropargyl alcohols in excellent yield. Naphthyl compounds is also effective for the transformation converted to 3z and 3ab in the yield of 94% and 96% respectively.

When 1-bromo-2-butyne (4a) was used instead of propargyl bromide, the rearrangement product allenyl alcohol was achieved with good yield under the same reaction conditions (Table 3). Importantly, the direct propargylation product was not detected in this catalytic system, which indicated that the chemo-selectivity for this reaction is quite good. For example, substrates (5a–5c) which substituted by isopropyl-, methyl- and fluoro- groups on the aromatic ring, reacted well and provided the corresponding products in moderate yields. In addition, heteroaromatic aldehyde (5d) is also worked for the transformation and an allenyl substituted alcohol (5e) was obtained with 85% yield.

To demonstrate the synthetic applications of our protocols, we tried to scale up the reaction of benzaldehyde (1a) with 3-bromo-1-propyne (2a) or 1-bromo-2-pentyne (4a) independently under standard conditions (Fig. 2). The corresponding products 3a or 5a was obtained in a gram-scale, which highlightened the potential applicability of this transformation in organic synthesis.

Fig. 2
figure 2

Gram-scale experiment

Full size image

Based on the above results and studies reported in the previous reference, a tentative mechanism for the Cu-Catalyzed, Mn-mediated propargylation and allenylation of aldehydes with propargyl bromides was proposed in Fig. 3 [52,53,54,55,56]. Mn, which is severed as a strong reducing agent, reduced the CuI to Cu0 in an active form in situ. Insertion of Cu0 to propargyl bromides gives the crucial intermediate progargyl metal species (Int-I) and allenyl metal species (Int-II). Then, nucleophilic addition of aldehydes conducted smoothly with metal species to deliver the Int-III and Int-IV. Finally, desired products were obtained in the presence of CF3COOH. The CuII complex was reduced to Cu0 with Mn powder to continue the next catalytic cycle.

Fig. 3
figure 3

Proposed mechanism

Full size image

In conclusion, the practical propargylation and allenylation of propargyl bromide has been discovered. The unique combination of the Cu catalyst and Mn powder present a novel and effective catalyst system in the preparation of homopropargylation alcohols and allenyl alcohols. Wide substrates compatibility has been exhibited with a variety of different substituent. This process represents a rare example of propargylation reaction and opens a new area of research. Further mechanistic studies and synthetic applications of this reaction are under progress in our laboratory.

Experiment

Procedure for the synthesis of homopropargyl alcohol

In a 10 mL Schlenk tube, aldehyde (0.5 mmol) was added to a stirred solution of 3-bromo-1-propyne (1.5 eq.), CuCl (10 mol%), Mn powder (3.0 eq.), and CF3COOH (25 mol%) in MeCN (2 mL) at room temperature under N2 atmosphere. After 24 h, the mixture was extracted with EtOAc (3 × 10 mL). The combined EtOAc layer was distilled and the crude product was then purified via column chromatograph.

Procedure for the synthesis of allenyl alchols

In a 10 mL Schlenk tube, aldehyde (0.5 mmol) was added to a stirred solution of 1-bromo-2-pentyne (1.5 eq.) (1.5 eq.), CuCl (10 mol%), Mn powder (3.0 eq.), and CF3COOH (25 mol%) in MeCN (2 mL) at room temperature under N2 atmosphere. After 24 h, the mixture was extracted with EtOAc (3 × 10 mL). The combined EtOAc layer was distilled and the crude product was then purified via column chromatograph.

1-phenylbut-3-yn-1-ol (3a) [57]

98% yield (71.6 mg), colourless oil. 1H NMR (400 MHz, CDCl3) δ 7.46–7.34 (m, 4H), 7.30 (ddd, J = 8.5, 3.6, 1.6 Hz, 1H), 4.88 (t, J = 5.4 Hz, 1H), 2.71–2.56 (m, 2H), 2.45 (s, 1H), 2.19–1.96 (m, 1H); 13C NMR (100 MHz, CDCl3) δ 142.4, 128.5, 128.0, 125.8, 80.7, 72.3, 71.0, 29.5.

1-(4-chlorophenyl)but-3-yn-1-ol (3b) [57]

96% yield (86.7 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.33–7.25 (m, 4H), 4.80 (t, J = 5.1 Hz, 1H), 2.81 (s, 1H), 2.58 (dd, J = 6.4, 2.5 Hz, 2H), 2.06 (dd, J = 3.4, 1.7 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 140.9, 133.7, 128.6, 127.2, 80.3, 71.6, 71.4, 29.4.

1-(p-tolyl)but-3-yn-1-ol (3c) [57]

91% yield (72.8 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.25 (d, J = 7.7 Hz, 2H), 7.14 (d, J = 7.7 Hz, 2H), 4.79 (s, 1H), 2.58 (dd, J = 11.1, 8.7 Hz, 3H), 2.33 (s, 3H), 2.03 (s, 1H). 13C NMR (100 MHz, CDCl3) δ 139.6, 137.7, 129.2, 125.8, 80.9, 72.2, 70.9, 29.3, 21.2.

1-(4-fluorophenyl)but-3-yn-1-ol (3d) [57]

97% yield (79.6 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.46–7.32 (m, 2H), 7.05 (t, J = 8.7 Hz, 2H), 4.86 (t, J = 5.5 Hz, 1H), 2.62 (dd, J = 6.3, 2.6 Hz, 2H), 2.49 (d, J = 2.5 Hz, 1H), 2.08 (t, J = 2.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 162.4 (d, J = 245 Hz), 138.2 (d, J = 3 Hz), 127.5 d, J = 8 Hz), 115.4 (d, J = 21 Hz), 80.4, 71.7, 71.2, 29.6.

1-(4-methoxyphenyl)but-3-yn-1-ol (3e) [57]

89% yield (78.4 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.29 (d, J = 8.6 Hz, 2H), 6.95–6.80 (m, 2H), 4.80 (t, J = 6.4 Hz, 1H), 3.79 (s, 3H), 2.64–2.58 (m, 2H), 2.05 (t, J = 2.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 159.3, 134.8, 127.1, 113.9, 80.9, 72.0, 70.9, 55.3, 29.3.

1-(4-isopropylphenyl)but-3-yn-1-ol (3f) [57]

89% yield (83.7 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.30 (d, J = 8.1 Hz, 2H), 7.21 (d, J = 8.2 Hz, 2H), 4.82 (s, 1H), 2.90 (dt, J = 13.8, 6.9 Hz, 1H), 2.62 (dd, J = 6.4, 2.6 Hz, 2H), 2.51 (s, 1H), 2.06 (t, J = 2.6 Hz, 1H), 1.24 (d, J = 6.9 Hz, 6H). 13C NMR (100 MHz, CDCl3) δ 148.7, 139.9, 126.6, 125.8, 81.0, 72.3, 70.9, 33.9, 29.3, 24.0.

1-(3-methoxyphenyl)but-3-yn-1-ol (3g) [57]

95% yield (83.6 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.27 (dd, J = 10.3, 5.9 Hz, 1H), 6.99–6.93 (m, 2H), 6.84 (ddd, J = 8.2, 2.5, 1.0 Hz, 1H), 4.85 (t, J = 6.3 Hz, 1H), 3.81 (s, 3H), 2.69–2.59 (m, 2H), 2.51 (s, 1H), 2.08 (t, J = 2.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 159.7, 144.2, 129.6, 118.1, 113.5, 111.3, 80.7, 72.3, 71.0, 55.3, 29.4.

1-(m-tolyl)but-3-yn-1-ol (3h) [57]

83% yield (66.5 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.24 (t, J = 7.5 Hz, 1H), 7.21–7.14 (m, 2H), 7.10 (d, J = 7.4 Hz, 1H), 4.82 (t, J = 6.4 Hz, 1H), 2.62 (dd, J = 6.4, 2.6 Hz, 2H), 2.51 (s, 1H), 2.35 (s, 3H), 2.06 (t, J = 2.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 142.5, 138.2, 128.8, 128.4, 126.4, 122.9, 80.9, 72.4, 70.9, 29.4, 21.5.

1-(2-chlorophenyl)but-3-yn-1-ol (3i) [57]

96% yield (86.4 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.62 (dd, J = 7.7, 1.4 Hz, 1H), 7.36–7.26 (m, 2H), 7.26–7.20 (m, 1H), 5.28 (dd, J = 7.8, 4.0 Hz, 1H), 2.80 (ddd, J = 16.9, 3.9, 2.7 Hz, 1H), 2.69 (s, 1H), 2.54 (ddd, J = 16.9, 7.8, 2.6 Hz, 1H), 2.10 (t, J = 2.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 139.7, 131.7, 129.4, 129.0, 127.1, 127.1, 80.3, 71.2, 68.7, 27.7.

1-(2-fluorophenyl)but-3-yn-1-ol (3j) [57]

95% yield (79.9 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.52 (td, J = 7.5, 1.5 Hz, 1H), 7.26 (ddd, J = 7.1, 4.6, 1.9 Hz, 1H), 7.16 (td, J = 7.5, 0.8 Hz, 1H), 7.02 (ddd, J = 10.4, 8.2, 0.9 Hz, 1H), 5.18 (dd, J = 7.2, 4.9 Hz, 1H), 2.74 (ddd, J = 16.8, 4.7, 2.6 Hz, 1H), 2.62 (ddd, J = 16.8, 7.6, 2.6 Hz, 2H), 2.07 (t, J = 2.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 160.0 (d, J = 244 Hz), 129.5, 129.3 (d, J = 8 Hz), 127.2 (d, J = 4 Hz), 124.3 (d, J = 3 Hz), 115.3 (d, J = 22 Hz), 80.3, 71.1, 66.4 (d, J = 2 Hz), 28.2.

1-(4-(trifluoromethyl)phenyl)but-3-yn-1-ol (3ak) [57]

75% yield (80.0 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.60 (d, J = 8.2 Hz, 2H), 7.49 (d, J = 8.1 Hz, 2H), 4.90 (t, J = 6.3 Hz, 1H), 2.83 (s, 1H), 2.65 – 2.59 (m, 2H), 2.08 (s, 1H). 13C NMR (100 MHz, CDCl3) δ 146.3, 130.0 (q, J = 32 Hz), 126.1, 125.4 (q, J = 4 Hz), 123.9 (q, J = 270 Hz), 79.9, 71.6 (d, J = 7 Hz), 29.4.

1-(4-propoxyphenyl)but-3-yn-1-ol (3l) [57]

85% yield (86.8 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.30 (d, J = 8.5 Hz, 2H), 6.88 (d, J = 8.5 Hz, 2H), 4.83 (t, J = 6.2 Hz, 1H), 3.91 (t, J = 6.6 Hz, 2H), 2.68–2.58 (m, 2H), 2.36 (s, 1H), 2.07 (d, J = 2.3 Hz, 1H), 1.80 (dd, J = 14.1, 7.0 Hz, 2H), 1.03 (t, J = 7.4 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 158.9, 134.4, 127.0, 114.4, 80.9, 72.1, 70.8, 69.5, 29.4, 22.6, 10.5.

1-(2,4-dimethylphenyl)but-3-yn-1-ol (3m) [57]

85% yield (74.0 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.36 (d, J = 7.9 Hz, 1H), 7.03 (d, J = 7.7 Hz, 1H), 6.95 (s, 1H), 5.04 (t, J = 6.4 Hz, 1H), 2.62–2.54 (m, 2H), 2.45 (d, J = 4.8 Hz, 1H), 2.30 (s, 3H), 2.29 (s, 3H), 2.05 (t, J = 2.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 137.6, 137.4, 134.6, 131.3, 127.0, 125.1, 81.1, 70.7, 68.8, 28.3, 21.0, 19.0.

1-(2,5-difluorophenyl)but-3-yn-1-ol (3n) [57]

94% yield (85.6 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.26 (ddd, J = 8.8, 5.8, 3.0 Hz, 1H), 7.10–6.79 (m, 2H), 5.24–5.07 (m, 1H), 2.83–2.48 (m, 3H), 2.10 (t, J = 2.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 158.9 (dd, J = 241, 2 Hz), 155.3 (dd, J = 238, 3 Hz), 131.2 (dd, J = 16, 7 Hz), 116.3 (dd, J = 24, 8 Hz), 115.5 (dd, J = 24, 9 Hz), 113.9 (dd, J = 25, 4 Hz), 79.7, 71.6, 65.9, 28.2 (d, J = 1 Hz).

1-(2,3-difluorophenyl)but-3-yn-1-ol (3o) [57]

87% yield (79.2 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.33–7.23 (m, 1H), 7.18–7.01 (m, 2H), 5.19 (dd, J = 6.9, 5.2 Hz, 1H), 2.82 (s, 1H), 2.74 (ddd, J = 16.8, 4.8, 2.6 Hz, 1H), 2.63 (ddd, J = 16.8, 7.4, 2.5 Hz, 1H), 2.08 (t, J = 2.5 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 150.2 (dd, J = 246, 12 Hz), 147.6 (dd, J = 246, 13), 131.9 (d, J = 10 Hz), 124.2 (dd, J = 7, 5 Hz), 121.8 (t, J = 3 Hz), 116.5 (d, J = 2 Hz), 79.8, 71.4, 66. 0 (t, J = 2 Hz), 28.2.

1-(2,3-dimethylphenyl)but-3-yn-1-ol (3p) [57]

87% yield (75.7 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.36 (d, J = 7.4 Hz, 1H), 7.17–7.04 (m, 2H), 5.15 (dd, J = 7.6, 5.0 Hz, 1H), 2.61–2.51 (m, 2H), 2.28 (s, 3H), 2.22 (s, 3H), 2.07 (d, J = 2.4 Hz, 1H), 1.97 (s, 1H). 13C NMR (100 MHz, CDCl3) δ 140.4, 137.0, 133.2, 129.4, 125.8, 122.9, 81.2, 70.7, 69.3, 28.3, 20.7, 14.7.

1-(2-methoxy-4-methylphenyl)but-3-yn-1-ol (3q) [57]

85% yield (80.8 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.25 (d, J = 7.6 Hz, 1H), 6.77 (d, J = 7.6 Hz, 1H), 6.68 (s, 1H), 5.09- 4.96 (m, 1H), 3.83 (d, J = 6.7 Hz, 3H), 2.98 (s, 1H), 2.67 (dddd, J = 24.2, 10.1, 6.3, 2.6 Hz, 2H), 2.34 (s, 3H), 2.03 (t, J = 2.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 156.2, 138.9, 127.4, 126.8, 121.2, 111.4, 81.5, 70.4, 68.9, 55.2, 27.5, 21.6.

1-(3-chloro-5-fluorophenyl)but-3-yn-1-ol (3r) [57]

95% yield (94.1 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.19 (s, 1H), 7.07–6.99 (m, 2H), 4.84 (t, J = 4.6 Hz, 1H), 2.65–2.61 (m, 1H), 2.59 (dd, J = 6.5, 3.0 Hz, 1H), 2.11 (t, J = 2.6 Hz, 1H), 1.68 (s, 1H). 13C NMR (100 MHz, CDCl3) δ 163.7 (d, J = 248 Hz), 146.2 (d, J = 7 Hz), 135.1 (d, J = 10 Hz), 121.9 (d, J = 4 Hz), 115.6 (d, J = 25 Hz), 111.4 (d, J = 22 Hz), 79.6, 71.8, 71.2 (d, J = 2 Hz), 29.4.

1-(4-fluoro-3-methoxyphenyl)but-3-yn-1-ol (3s) [57]

88% yield (85.4 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.09–7.01 (m, 2H), 6.88 (ddd, J = 8.3, 4.3, 2.1 Hz, 1H), 4.83 (t, J = 6.3 Hz, 1H), 3.89 (d, J = 5.9 Hz, 3H), 2.62 (dd, J = 6.4, 2.6 Hz, 2H), 2.55 (s, 1H), 2.09 (t, J = 2.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 151.914.7 (d, J = 244 Hz), 147.6 (d, J = 11 Hz), 138.8 (d, J = 3 Hz), 118.1 (d, J = 7 Hz), 115.8 (d, J = 19 Hz), 110.9 (d, J = 2 Hz), 80.4, 71.9, 71.3, 56.2, 29.6.

1-(4-fluoro-3-methylphenyl)but-3-yn-1-ol (3t) [57]

88% yield (78.4 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.24–7.08 (m, 2H), 6.97 (t, J = 8.9 Hz, 1H), 4.81 (t, J = 6.3 Hz, 1H), 2.61 (dd, J = 6.3, 2.4 Hz, 2H), 2.45 (s, 1H), 2.27 (s, 3H), 2.08 (s, 1H). 13C NMR (100 MHz, CDCl3) δ 160.9 (d, J = 243 Hz), 137.87, 128.9 (d, J = 2 Hz), 125.0, 124.7(d, J = 8 Hz), 114.9 (d, J = 22 Hz), 80.6, 71.8, 71.1, 29.5, 14.7(d, J = 4 Hz).

2-(benzo[d][1,3]dioxol-4-yl)but-3-yn-1-ol (3u) [57]

85% yield (80.8 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 6.95–6.89 (m, 1H), 6.84 (t, J = 7.8 Hz, 1H), 6.78 (dd, J = 7.6, 1.0 Hz, 1H), 5.96 (dd, J = 9.2, 1.1 Hz, 2H), 4.98 (dd, J = 10.2, 6.3 Hz, 1H), 2.84–2.58 (m, 3H), 2.06 (t, J = 2.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 147.4, 144.1, 124.1, 121.8, 119.3, 108.2, 101.0, 80.5, 70.9, 68.3, 27.6.

1-(thiophen-2-yl)but-3-yn-1-ol (3v) [57]

88% yield (66.9 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.32–7.22 (m, 1H), 6.99 (ddd, J = 11.1, 6.1, 2.5 Hz, 2H), 5.11 (d, J = 3.7 Hz, 1H), 2.79–2.68 (m, 3H), 2.11 (dd, J = 5.2, 2.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 146.2, 126.7, 125.0, 124.2, 80.1, 71.5, 68.5, 29.5.

1-(4-chloropyridin-2-yl)but-3-yn-1-ol (3w) [57]

93% yield (84.1 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 8.46 (d, J = 5.3 Hz, 1H), 7.49 (d, J = 1.7 Hz, 1H), 7.26 (dd, J = 5.4, 2.0 Hz, 1H), 4.88 (t, J = 6.0 Hz, 1H), 2.78–2.65 (m, 2H), 2.06 (t, J = 2.6 Hz, 1H), 1.25 (s, 1H). 13C NMR (100 MHz, CDCl3) δ 162.0, 149.4, 144.9, 123.3, 121.2, 80.0, 71.3, 71.1, 28.2.

1-(pyridin-3-yl)but-3-yn-1-ol (3x) [57]

95% yield (69.9 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 8.54 (d, J = 2.0 Hz, 1H), 8.47 (dd, J = 4.8, 1.5 Hz, 1H), 7.79 (dt, J = 7.9, 1.8 Hz, 1H), 7.33–7.26 (m, 1H), 4.92 (t, J = 6.4 Hz, 1H), 2.70–2.65 (m, 2H), 2.08 (t, J = 2.6 Hz, 1H), 1.35–1.23 (m, 1H). 13C NMR (100 MHz, CDCl3) δ 148.9, 147.6, 138.3, 133.9, 123.5, 79.9, 71.5, 70.0, 29.3.

1-(quinolin-2-yl)but-3-yn-1-ol (3y) [57]

93% yield (92.0 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 8.19 (d, J = 8.5 Hz, 1H), 8.09 (d, J = 8.5 Hz, 1H), 7.85 (d, J = 8.1 Hz, 1H), 7.73 (dd, J = 8.4, 1.4 Hz, 1H), 7.59–7.49 (m, 2H), 5.07 (t, J = 5.9 Hz, 1H), 2.80 (ddd, J = 5.9, 2.5, 1.7 Hz, 2H), 2.02 (t, J = 2.7 Hz, 1H), 1.25 (s, 1H). 13C NMR (100 MHz, CDCl3) δ 160.0, 146.5, 137.0, 129.9, 128.9, 127.8, 127.7, 126.7, 118.5, 80.5, 71.0, 71.0, 28.3.

1-(naphthalen-2-yl)but-3-yn-1-ol (3z) [57]

94% yield (92.5 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.87–7.70 (m, 4H), 7.56–7.36 (m, 3H), 4.98 (t, J = 6.3 Hz, 1H), 2.75 (s, 1H), 2.69 (dd, J = 6.4, 2.6 Hz, 2H), 2.05 (t, J = 2.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 139.9, 133.2, 133.2, 128.4, 128.1, 127.8, 126.3, 126.1, 124.8, 123.8, 80.8, 72.5, 71.2, 29.4.

1-(naphthalen-1-yl)but-3-yn-1-ol (3ab) [57]

96% yield (94.1 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 8.04 (d, J = 8.2 Hz, 1H), 7.89–7.83 (m, 1H), 7.79 (d, J = 8.2 Hz, 1H), 7.69 (d, J = 7.2 Hz, 1H), 7.54–7.44 (m, 3H), 5.63 (dd, J = 8.2, 4.2 Hz, 1H), 2.87 (ddd, J = 17.0, 4.2, 2.7 Hz, 1H), 2.73 (ddd, J = 17.0, 8.2, 2.6 Hz, 2H), 2.12 (t, J = 2.6 Hz, 1H). 13C NMR (100 MHz, CDCl3) δ 137.8, 133.8, 130.2, 129.1, 128.5, 126.3, 125.7, 125.4, 123.0, 122.8, 81.0, 71.3, 69.3, 28.7.

1-(4-isopropylphenyl)-2-methyl-3λ5-buta-2,3-dien-1-ol (5a) [57]

76% yield (76.8 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.30 (d, J = 8.0 Hz, 2H), 7.21 (d, J = 8.0 Hz, 2H), 5.07 (s, 1H), 4.96–4.85 (m, 2H), 2.90 (dt, J = 13.8, 6.9 Hz, 1H), 2.18 (s, 1H), 1.58 (t, J = 3.0 Hz, 3H), 1.24 (d, J = 7.0 Hz, 6H).13C NMR (100 MHz, CDCl3) δ 204.6, 148.6, 139.2, 126.6, 126.5, 102.7, 77. 9, 74.5, 33.9, 24.0, 14.7.

2-methyl-1-(p-tolyl)-3λ5-buta-2,3-dien-1-ol (5b) [57]

83% yield (54.9 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.25 (d, J = 8.0 Hz, 2H), 7.15 (d, J = 7.9 Hz, 2H), 5.05 (s, 1H), 4.96–4.82 (m, 2H), 2.34 (s, 3H), 2.30 (s, 1H), 1.56 (t, J = 3.1 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 204.7, 138.9, 137.5, 129.1, 126. 6, 102.7, 77.8, 74.5, 21.2, 14.7.

1-(4-fluorophenyl)-2-methyl-3λ5-buta-2,3-dien-1-ol (5c) [57]

73% yield (73 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.34 (dd, J = 8.4, 5.6 Hz, 2H), 7.03 (t, J = 8.7 Hz, 2H), 5.08 (s, 1H), 4.93–4.86 (m, 2H), 2.39 (s, 1H), 1.55 (t, J = 3.1 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 162.3(d, J = 244 Hz), 137.5 (d, J = 3 Hz), 128.3 (d, J = 8 Hz), 115.2 (d, J = 21 Hz), 102.6, 78.1, 77.4, 74.0, 14.5.

2-methyl-1-(thiophen-2-yl)-3λ5-buta-2,3-dien-1-ol (5d) [57]

76% yield (63.1 mg), colorless oil. 1H NMR (400 MHz, CDCl3) δ 7.29–7.25 (m, 1H), 7.02 (d, J = 3.1 Hz, 1H), 6.99–6.95 (m, 1H), 5.35 (s, 1H), 4.99–4.86 (m, 2H), 2.34 (d, J = 4.4 Hz, 1H), 1.69 (t, J = 3.0 Hz, 3H). 13C NMR (100 MHz, CDCl3) δ 204.4, 146.1, 126.6, 125.2, 125.0, 102.6, 78.6, 70.7, 14.7.

Conclusions

In conclusion, we have established the first Cu-catalyzed, Mn-mediated propargylation and allenylation of aldehydes with propargyl bromides. The unique combination of the Cu catalyst and Mn powder present a novel and effective catalyst system in the preparation of homopropargylation alcohols and allenyl alcohols. The overall transformation is highly efficient with mild conditions, large substrate scope, and excellent chem-selectivity.

Availability of data and materials

All data generated or analyzed during this study are included in this published and its Additional file 1.

References

  1. Alami M, Hamze A, Provot O. Hydrostannation of alkynes. ACS Catal. 2019;9:3437.

    Article  CAS  Google Scholar 

  2. Parker KDJ, Fryzuk MD. Synthesis, structure, and reactivity of Niobium and Tantalum alkyne complexes. Organometallics. 2015;34:2037.

    Article  CAS  Google Scholar 

  3. Corpas J, Mauleón P, Gómez Arrayá M, Carretero JC. Transition-metal-catalyzed functionalization of alkynes with organoboron reagents: new trends, mechanistic insights, and applications. ACS Catal. 2021;11:7513.

    Article  CAS  Google Scholar 

  4. Gilmore K, Alabugin IV. Cyclizations of Alkynes: Revisiting Baldwin’s rules for ring closure. Chem Rev. 2011;111:6513.

    Article  CAS  PubMed  Google Scholar 

  5. Liu L, Ward RM, Schomaker JM. Mechanistic aspects and synthetic applications of radical additions to allenes. Chem Rev. 2019;119:12422.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  6. Blieck R, Taillefer M, Monnier F. Metal-catalyzed intermolecular hydrofunctionalization of allenes: easy access to allylic structures via the selective formation of C-N, C–C, and C–O Bonds. Chem Rev. 2020;120:13545.

    Article  CAS  PubMed  Google Scholar 

  7. Zhai R, Xue Y, Liang T, Mi J, Xu Z. Regioselective arene and heteroarene functionalization: N-Alkenoxypyridinium salts as electrophilic alkylating agents for the synthesis of α-aryl/α-heteroaryl ketones. J Org Chem. 2018;83:10051.

    Article  CAS  PubMed  Google Scholar 

  8. Baran PS, Shenvi RA. Total synthesis of (±)-Chartelline C. J Am Chem Soc. 2006;128:14028.

    Article  CAS  PubMed  Google Scholar 

  9. Farahat AA, Kumar A, Say M, Barghash AEM, Goda FE, Eisa HM, Wenzler T, Brun R, Liu Y, Mickelson L, Wilson WD, Boykin DW. Synthesis, DNA binding, fluorescence measurements and antiparasitic activity of DAPI related diamidines. Bioorg Med Chem. 2010;18:557.

    Article  CAS  PubMed  Google Scholar 

  10. Grover HK, Lebold TP, Kerr MA. Tandem Cyclopropane ring-opening/Conia-ene reactions of 2-alkynyl indoles: A [3 + 3] annulative route to tetrahydrocarbazoles. Org Lett. 2011;13:220.

    Article  CAS  PubMed  Google Scholar 

  11. Zhang W, Ready JM. A concise total synthesis of dictyodendrins F, H, and I using aryl ynol ethers as key building blocks. J Am Chem Soc. 2016;138:10684.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  12. Praveen C, Ananth DB. Design, synthesis and cytotoxicity of pyrano[4,3-b]indol-1(5H)-ones: A hybrid pharmacophore approach via gold catalyzed cyclization. Bioorg Med Chem Lett. 2016;26:2507.

    Article  CAS  PubMed  Google Scholar 

  13. Brasholz M, Reissig HU, Zimmer R. Sugars, alkaloids, and heteroaromatics: exploring heterocyclic chemistry with alkoxyallenes. Acc Chem Res. 2009;42:45.

    Article  CAS  PubMed  Google Scholar 

  14. Urgoita G, San Martin R, Teresa Herrero M, Domínguez E. Aerobic cleavage of alkenes and alkynes into carbonyl and carboxyl compounds. ACS Catal. 2017;7:3050.

    Article  Google Scholar 

  15. Chinchilla R, Nájera C. Chemicals from alkynes with palladium catalysts. Chem Rev. 2014;114:1783.

    Article  CAS  PubMed  Google Scholar 

  16. Lin W, Ma S. Enantioselective synthesis of naturally occurring isoquinoline alkaloids: (S)-(−)-trolline and (R)-(+)-oleracein E. Org Chem Front. 2017;4:958.

    Article  CAS  Google Scholar 

  17. Lu T, Lu Z, Ma ZX, Zhang Y, Hsung RP. Allenamides: A powerful and versatile building block in organic synthesis. Chem Rev. 2013;113:4862.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  18. Han Y, Ma S. Rhodium-catalyzed highly diastereoselective intramolecular [4 + 2] cycloaddition of 1,3-disubstituted allene-1,3-dienes. Org Chem Front. 2018;5:2680.

    Article  CAS  Google Scholar 

  19. Li QH, Jiang X, Wu K, Luo RQ, Liang M, Zhang ZH, Huang ZY. Research progress on the catalytic enantioselective synthesis of axially chiral allenes by chiral organocatalysts. Curr Org Chem. 2020;24:694.

    Article  CAS  Google Scholar 

  20. Shao XB, Zhang Z, Li QH, Zhao ZG. Synthesis of multi-substituted allenes from organoalane reagents and propargyl esters by using a nickel catalyst. Org Biomol Chem. 2018;16:4797.

    Article  CAS  PubMed  Google Scholar 

  21. Shao X, Wen C, Zhang G, Cao K, Wu L, Li QJ. Palladium-catalyzed, ligand-free SN2’ substitution reactions of organoaluminum with propargyl acetates for the synthesis of multi-substituted allenes. Organomet Chem. 2018;870:68.

    Article  CAS  Google Scholar 

  22. Zhang Z, Shao XB, Zhang G, Li Q, Li X. Highly efficient synthesis of multi-substituted allenes from propargyl acetates and organoaluminum reagents mediated by palladium. Synthesis. 2017;493:643.

    Google Scholar 

  23. Zhang Z, Mo S, Zhang G, Shao X, Li Q, Zhong Y. Synthesis of multisubstituted allenes via Palladium-catalyzed cross-coupling reaction of propargyl acetates with an organoaluminum reagent. Synlett. 2017;5:611.

    Google Scholar 

  24. Panek JS. Comprehensive organic synthesis. Oxford: Pergamon Press; 1991. p. 595.

    Google Scholar 

  25. Yamamoto H. Comprehensive organic synthesis. Oxford: Pergamon Press; 1991. p. 81.

    Book  Google Scholar 

  26. Yamaguchi M. Main group metals in organic synthesis. New York: Wiley-VCH. Weinheim; 2004. p. 307.

    Google Scholar 

  27. Smith MB, March J. March’s advanced organic chemistry: Reactions, mechanisms, and structure, 6th (Ed), Jon Wiley and Sons, Inc.: New York, 2006; 752.

  28. Yamamoto H. In Comprehensive organic synthesis. New York: Pergamon Press; 1991. p. 81.

    Book  Google Scholar 

  29. Isaac MB, Chan TH. Indium-mediated coupling of aldehydes with prop-2-ynyl bromides in aqueous media. J Chem Soc Chem Commun. 1995;1003:89.

    Google Scholar 

  30. Loh TP, Lin MJ, Tan KL. Indium-mediated propargylation of aldehydes: regioselectivity and enantioselectivity studies. Tetrahedron Lett. 2003;44:507.

    Article  CAS  Google Scholar 

  31. Haddad TD, Hirayama LC, Buckley JJ, Singaram BJ. Indium-mediated asymmetric Barbier-type propargylations: additions to aldehydes and ketones and mechanistic investigation of the organoindium reagents. Org Chem. 2012;77:889.

    Article  CAS  Google Scholar 

  32. Hojo M, Harada H, Ito H, Hosomi A. A new type of allyl- and prop-2-ynyl-manganese species: generation and reactions with electrophiles. Chem Commun. 1997;21:2077.

    Article  Google Scholar 

  33. Zha ZG, Hui AL, Zhou YQ, Miao Q, Wang ZY, Zhang HC. A Recyclable Electrochemical Allylation in Water. Org Lett. 2005;7:1903.

    Article  CAS  PubMed  Google Scholar 

  34. López-Martínez JL, Torres-García I, Rodríguez-García I, Muñoz-Dorado M, Álvarez-Corral M. Stereoselective Barbier-Type allylations and propargylations mediated by CpTiCl3. J Org Chem. 2019;84:806.

    Article  PubMed  Google Scholar 

  35. Hojo M, Sakuragi R, Okabe S, Hosomi A. Allyl- and propargylchromium reagents generated by a chromium(III) ate-type reagent as a reductant and their reactions with electrophiles. Chem Commun. 2001;357:8.

    Google Scholar 

  36. Han Y, Chi Z, Huang YZ. Gallium-mediated highly regioselective reaction of allyl-type bromide and propargyl-type bromide with aldehyde. Synth Commun. 1999;29:1287.

    Article  CAS  Google Scholar 

  37. Zha ZG, Qiao S, Jiang JY, Wang YS, Miao Q, Wang ZY. Barbier-type reaction mediated with tin nano-particles in water. Tetrahedron. 2005;61:2521.

    Article  CAS  Google Scholar 

  38. Bieber LW, da Silva MF, da Costa RC, Silva LOS. Zinc barbier reaction of propargyl halides in water. Tetrahedron Lett. 1998;39:3655.

    Article  CAS  Google Scholar 

  39. Fandrick DR, Reeves JT, Bakonyi J, Nyalapatla PR. Zinc catalyzed and mediated asymmetric propargylation of trifluoromethyl ketones with a propargyl boronate. J Org Chem. 2013;78:3592.

    Article  CAS  PubMed  Google Scholar 

  40. Iseki K, Kuroki Y, Kobayashi Y. Asymmetric allenylation of aliphatic aldehydes catalyzed by a chiral formamide. Tetrahedron Asymmetry. 1998;9:2889.

    Article  CAS  Google Scholar 

  41. Evans DA, Sweeney ZK, Rovis T, Tedrow JS. Highly enantioselective syntheses of homopropargylic alcohols and dihydrofurans catalyzed by a bis(oxazolinyl)pyridine−Scandium triflate complex. J Am Chem Soc. 2001;123:12095.

    Article  CAS  PubMed  Google Scholar 

  42. Marshall JA, Gung BW, Grachan ML. Synthesis and reactions of allenylmetal compounds. In: Modern Allene Chemistry; (Ed.) Wiley-VCH: Weinheim, 2004; 493.

  43. Thaima T, Zamani F, Hyland CJT, Pyne SG. Allenylation and propargylation reactions of ketones, aldehydes, imines, and iminium ions using organoboronates and related derivatives. Synthesis. 2017;49:1461.

    Article  CAS  Google Scholar 

  44. Denmark SD, Fu J. Catalytic enantioselective addition of allylic organometallic reagents to aldehydes and ketones. Chem Rev. 2003;103:2763.

    Article  CAS  PubMed  Google Scholar 

  45. Ma X, Li S, Devaramani S, Zhao G, Xu D. One-pot, regioselective synthesis of homopropargyl alcohols using propargyl bromide and carbonyl compound by the Mg-mediated reaction under solvent-free conditions. Lett Org Chem. 2020;17:438.

    Article  CAS  Google Scholar 

  46. Wendlandt AE, Suess AM, Stahl SS. Copper-catalyzed aerobic oxidative C-H functionalizations: trends and mechanistic insights. Angew Chem Int Ed. 2011;50:11062.

    Article  CAS  Google Scholar 

  47. McCann SD, Stahl SS. Copper-catalyzed aerobic oxidations of organic molecules: pathways for two-electron oxidation with a four-electron oxidant and a one-electron redox-active catalyst. Acc Chem Res. 2015;48:1756.

    Article  CAS  PubMed  Google Scholar 

  48. Allen SC, Walvoord RR, Padilla-Salinas R, Kozlowski MC. Aerobic copper-catalyzed organic reactions. Chem Rev. 2013;113:6234.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  49. Guo XX, Gu DW, Wu Z, Zhang W. Copper-catalyzed C-H functionalization reactions: efficient synthesis of heterocycles. Chem Rev. 2015;115:1622.

    Article  CAS  PubMed  Google Scholar 

  50. Crossley SWM, Obradors C, Martinez RM, Shenvi RA. Mn-, Fe-, and Co-catalyzed radical hydrofunctionalizations of olefins. Chem Rev. 2016;116:8912.

    Article  CAS  PubMed  PubMed Central  Google Scholar 

  51. Irrgang T, Kempe R. 3d-Metal catalyzed N- and C-alkylation reactions via borrowing hydrogen or hydrogen autotransfer. Chem Rev. 2019;119:2524.

    Article  CAS  PubMed  Google Scholar 

  52. Durandetti M, Périchon J. A simple practical method for the synthesis of 4,6-dimethoxy-1,3,5-triazin-2(1H)-one using dimethylamine-functionalized solid-phase reagents. Synthesis. 2009;1:542.

    Google Scholar 

  53. Chattopadhyay A, Kr DA. A simple and efficient procedure of low valent iron- or copper-mediated reformatsky reaction of aldehydes. J Org Chem. 2007;72:9357.

    Article  CAS  PubMed  Google Scholar 

  54. Hojo M, Harada H, Cto H, Hosomi A. Manganese ate complexes as new reducing agents: perfectly regiocontrolled generation and reactions of the manganese enolates with electrophiles. J Am Chem Soc. 1997;119:5459.

    Article  CAS  Google Scholar 

  55. Suh S, Rieke RD. Synthesis of β-hydroxy esters using highly active manganese. Tetrahedron Lett. 2004;45:1807.

    Article  CAS  Google Scholar 

  56. Liu XY, Li XR, Zhang R, Chu XQ, Rao W, Loh TP, Shen ZL. Iron(0)-mediated reformatsky reaction for the synthesis of β-hydroxyl carbonyl compounds. Org Lett. 2019;21:5873.

    Article  CAS  PubMed  Google Scholar 

  57. Mori-Quiroz LM, Maloba EW, Maleczka RE. Silylcyclopropanes by selective [1,4]-Wittig rearrangement of 4-silyl-5,6-dihydropyrans. Org Lett. 2021;23:5724.

    Article  CAS  PubMed  Google Scholar 

Download references

Acknowledgements

Not applicable.

Funding

The authors thank the National Natural Science Foundation of China (22161003) and the Project of Science and Technology of Xuzhou Government (No. KC16SG250).

Author information

Authors and Affiliations

  1. Xuzhou Medical University, Tongshan Road 209, Xuzhou, 221004, China

    Rongli Zhang & Yuchen Yan

  2. School of Pharmaceutical Sciences, Gannan Medical University, Ganzhou, 341000, China

    Yanping Xia & Lu Ouyang

Authors
  1. Rongli Zhang
    View author publications

    You can also search for this author in PubMed Google Scholar

  2. Yanping Xia
    View author publications

    You can also search for this author in PubMed Google Scholar

  3. Yuchen Yan
    View author publications

    You can also search for this author in PubMed Google Scholar

  4. Lu Ouyang
    View author publications

    You can also search for this author in PubMed Google Scholar

Contributions

ZRL contributed to the conception of the study. XY and OL performed the experiment. ZRL and YYC contributed to analysis and manuscript preparation. All authors read and approved the final manuscript.

Corresponding authors

Correspondence to Rongli Zhang or Lu Ouyang.

Ethics declarations

Ethics approval and consent to participate

Not applicable.

Consent for publication

Not applicable.

Competing interests

The authors declare no competing interests.

Additional information

Publisher's Note

Springer Nature remains neutral with regard to jurisdictional claims in published maps and institutional affiliations.

Supplementary Information

13065_2022_803_MOESM1_ESM.doc

Additional file 1.

Rights and permissions

Open Access This article is licensed under a Creative Commons Attribution 4.0 International License, which permits use, sharing, adaptation, distribution and reproduction in any medium or format, as long as you give appropriate credit to the original author(s) and the source, provide a link to the Creative Commons licence, and indicate if changes were made. The images or other third party material in this article are included in the article's Creative Commons licence, unless indicated otherwise in a credit line to the material. If material is not included in the article's Creative Commons licence and your intended use is not permitted by statutory regulation or exceeds the permitted use, you will need to obtain permission directly from the copyright holder. To view a copy of this licence, visit http://creativecommons.org/licenses/by/4.0/. The Creative Commons Public Domain Dedication waiver (http://creativecommons.org/publicdomain/zero/1.0/) applies to the data made available in this article, unless otherwise stated in a credit line to the data.

Reprints and Permissions

About this article

Check for updates. Verify currency and authenticity via CrossMark

Cite this article

Zhang, R., Xia, Y., Yan, Y. et al. Cu-catalyzed, Mn-mediated propargylation and allenylation of aldehydes with propargyl bromides. BMC Chemistry 16, 14 (2022). https://doi.org/10.1186/s13065-022-00803-3

Download citation

  • Received:

  • Accepted:

  • Published:

  • DOI: https://doi.org/10.1186/s13065-022-00803-3

Keywords

  • Propargylation
  • Allenylation
  • Mn powder
  • Cu-catalyzed
  • Gram scale

BMC Chemistry

ISSN: 2661-801X

Contact us