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CN102153472B - Method for synthesizing 1,3 (E)-diene-2-carboxylic ester compounds - Google Patents

Method for synthesizing 1,3 (E)-diene-2-carboxylic ester compounds Download PDF

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CN102153472B
CN102153472B CN201110050542.6A CN201110050542A CN102153472B CN 102153472 B CN102153472 B CN 102153472B CN 201110050542 A CN201110050542 A CN 201110050542A CN 102153472 B CN102153472 B CN 102153472B
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carboxylicesters
diene
rhodium chloride
alcohol
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CN102153472A (en
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麻生明
傅春玲
张小兵
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Zhejiang University ZJU
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Zhejiang University ZJU
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Abstract

The invention discloses a method for synthesizing 1,3 (E)-diene-2-carboxylic ester compounds. By rearrangement reaction of 1,3- ester group on various substituted 2,3-allenoic acid carboxylic esters under the catalysis of tri(triphenylphosphorus)-rhodium chloride or bi(triphenylphosphorus) carbonyl-rhodium chloride, a series of 1,3 (E)-diene-2-carboxylic ester compounds of various substitution anti-form are generated. The method is simple to operate, materials and agents are easy to obtain, the reaction has high yield, forward-backward selectivity is good, the product is easy to separate and purify, and the method is applicable to various substituted 1,3 (E)-diene-2-carboxylic esters.

Description

The method of the carboxylicesters of a kind of synthetic 1,3 (E)-diene-2-alcohol
Technical field
The present invention relates to a kind of synthetic 1,3 ( ethe method of)-diene-2-carboxylicesters, by 2 of various replacements, the rearrangement reaction of 1,3-ester group occurs in 3-connection enol carboxylicesters under three (triphenyl phosphorus) RHODIUM CHLORIDE or the catalysis of two (triphenyl phosphorus) carbonyl RHODIUM CHLORIDE, generate a series of various replacements 1,3 ( ethe method of)-diene-2-carboxylic acid ester compound.
Background technology
1,3 ( e)-diene-2-carboxylicesters is one of intermediate important in organic synthesis, is also one of structural unit common in natural product, at aspects such as biological technical field, medicine and agricultural chemicals, huge value of exploiting and utilizing is arranged.In document, mostly the synthetic of this compounds is to synthesize by eneyne or ketenes, but severe reaction conditions to be used strong acid and strong base or hypertoxic catalyzer mercury before.Not long ago ester group rearrangement reaction (Buzas, the A. K. of golden catalysis have been reported in document; Istrate, F. M.; Gagosz, F. org. Lett. 2007, 9, 985.), but the cri-trans selectivity of this method is poor, not high to the universality of raw material.This patent provides 2 of a kind of rhodium catalysis, and the rearrangement reaction of 1,3-ester group occurs 3-connection enol carboxylicesters, highly selective obtain 1,3 ( ethe method of)-diene-2-carboxylicesters.
Summary of the invention
Purpose of the present invention just be to provide a kind of under simple condition, utilize the rearrangement reaction of 1,3-ester group effectively synthetic various replacements 1,3 ( ethe method of)-diene-2-carboxylates derivatives, the cri-trans selectivity of reaction is high, has substrate universality preferably.
Concrete technical scheme of the present invention is as follows:
The present invention be a kind of synthetic 1,3 ( ethe method of)-diene-2-carboxylic acid ester compound, by 2,3-connection enol carboxylicesters 1under three (triphenyl phosphorus) RHODIUM CHLORIDE or the catalysis of two (triphenyl phosphorus) carbonyl RHODIUM CHLORIDE, the rearrangement reaction of 1,3-ester group occurs, highly selective generation 1,3 ( e)-diene-2-carboxylicesters 2, reaction formula is as follows:
Figure 2011100505426100002DEST_PATH_IMAGE001
R 1=alkyl, aryl; R 2=hydrogen, alkyl, aryl base or allyl group; R 3=alkyl, aryl or alkoxyl group; The steps include:
(1), 2,3-connection enol carboxylicesters 1under three (triphenyl phosphorus) RHODIUM CHLORIDE or the catalysis of two (triphenyl phosphorus) carbonyl RHODIUM CHLORIDE, the rearrangement reaction of 1,3-ester group occurs, generate trans 1,3 ( e)-diene-2-carboxylicesters 2: at a certain temperature, by catalyzer, 2,3-connection enol carboxylicesters 1add in reaction flask the reaction certain hour;
(2), after step (1) reacts completely, through concentrated, rapid column chromatography, obtain product 1,3 ( e)-diene-2-carboxylicesters 2.
Of the present invention 1,3 ( e)-diene-2-carboxylicesters 2can on the 3-position, phenyl be arranged, butyl or allyl group substituting group.
Of the present invention 2,3-connection enol carboxylicesters 1: catalyzer: toluene=1 mmole: 0.01-0.10 mmole: 6 milliliters.
The present invention relates to a kind of various replacements 1,3 ( ethe synthetic method of)-diene-2-carboxylic acid ester compound, i.e. 2 of various replacements, 3-connection enol carboxylicesters 1under three (triphenyl phosphorus) RHODIUM CHLORIDE or the catalysis of two (triphenyl phosphorus) carbonyl RHODIUM CHLORIDE, the rearrangement reaction of 1,3-ester group occurs, generate a series of various replacements trans 1,3 ( e)-diene-2-carboxylic acid ester compound, present method is simple to operate, raw material and reagent are easy to get, reaction yield is high, the cri-trans selectivity of reaction is good, easily separated purifying, be applicable to synthetic various replacements 1,3 ( e)-diene-2-carboxylic acid ester compound is synthetic.
The present invention has overcome the drawback of traditional method, has the following advantages: 1) raw material is simple and easy to get, easy to prepare; 2) mild condition, strong operability; 3) the substrate universality is high, can synthesize various replacements 1,3 ( e)-diene-2-carboxylicesters; 4) cri-trans selectivity of reaction is high; 5) the easily separated purifying of product.
The present invention be applicable to various replacements 1,3 ( e)-diene-2-carboxylicesters 2, and can obtain the compound that transconfiguration is the master, be to the significant improvement of reaction in the past.
Innovative point of the present invention has been to develop 2 of a kind of rhodium catalysis, 1,3 ester group migration of 3-connection enol.
Present method gained corresponding 1,3 ( ethe productive rate of)-diene-2-carboxylicesters is 49-92%, along reverse proportionality, is>96/4->99/1.
Embodiment
Following examples contribute to understand the present invention, but are not limited to content of the present invention.
embodiment 1
Add three (triphenyl phosphorus) RHODIUM CHLORIDE (4.7 mg in reaction tubes, 0.005 mmol, 1 mol%), triphenyl phosphorus (3.6 mg, 0.014 mmol, 3 mol%), 3-butyl-3,4-pentadiene-2-base acetic ester (90.6 mg, 0.5 mmol), toluene (3 mL). reaction tubes is placed in 120 degree oil baths. after TLC follows the tracks of and reacts completely, concentrated, rapid column chromatography (eluent: petroleum ether/ethyl ether=80/1) obtain product 3-butyl-1,3 ( e)-pentadiene-2-base acetic ester (73.8 mg, 81%): liquid.
1H NMR (300 MHz, CDCl 3) δ 5.74 (q, J = 7.1 Hz, 1 H, CH=), 5.04-5.00 (s like m, 1 H, one of CH 2=), 4.77-4.73 (s like m, 1 H, one of CH 2=), 2.29-2.18 (m, 5 H, CH 2 + CH 3), 1.72 (d, J = 6.6 Hz, 3 H, CH 3), 1.50-1.24 (m, 4 H, 2 × CH 2), 0.93 (t, J = 7.1 Hz, 3 H, CH 3); 13C NMR (CDCl 3, 75 MHz) δ 169.1, 153.7, 134.0, 123.1, 100.8, 30.7, 26.9, 22.8, 20.9, 13.9, 13.7; IR (neat, cm -1) 2958, 2873, 1766, 1644, 1614, 1466, 1369, 1217, 1196, 1139, 1019; MS (EI) m/z (%) 182 (M +, 5.17), 125 (100); HRMS Calcd for C 11H 18O 2 (M +): 182.1307, Found: 182.1307.
embodiment 2
Press the described method of embodiment 1, different is that substrate used and reagent are: three (triphenyl phosphorus) RHODIUM CHLORIDE (4.6 mg, 0.005 mmol, 1 mol%), triphenyl phosphorus (4.1 mg, 0.016 mmol, 3 mol%), 3-butyl-6-methyl isophthalic acid, 2-heptadiene-4-base acetic ester (126.5 mg, 0.5 mmol), toluene (3 mL) obtains product 3-butyl-6-methyl isophthalic acid, 3 ( e)-heptadiene-2-base acetic ester (113.0 mg, 89%): liquid.
1H NMR (300 MHz, CDCl 3) δ 5.62 (t, J = 7.4 Hz, 1 H, CH=), 5.02 (d, J = 1.8 Hz, 1 H, one of CH 2=), 4.76 (d, J = 1.8 Hz, 1 H, one of CH 2=), 2.26-2.19 (m, 5 H, CH 2 + CH 3), 2.14-2.05 (m, 2 H, CH 2), 1.49-1.22 (m, 12 H, 6 × CH 2), 0.96-0.84 (m, 6 H, 2 × CH 3); 13C NMR (CDCl 3, 75 MHz) δ 169.1, 153.7, 132.9, 129.3, 100.9, 31.7, 31.1, 29.4, 29.1, 28.1, 27.3, 22.9, 22.6, 20.9, 14.0, 13.9; IR (neat, cm -1) 2957, 2928, 2858, 1767, 1642, 1614, 1467, 1368, 1216, 1197, 1141, 1019; MS (EI) m/z (%) 252 (M +, 4.62), 125 (100); HRMS Calcd for C 16H 28O 2 (M +): 252.2089, Found: 252.2090.
embodiment 3
Press the described method of embodiment 1, different is that substrate used and reagent are: three (triphenyl phosphorus) RHODIUM CHLORIDE (4.9 mg, 0.005 mmol, 1 mol%), triphenyl phosphorus (4.0 mg, 0.015 mmol, 3 mol%), 3-butyl-1,2-decadiene-5-alkynes-4-base acetic ester (110.3 mg, 0.5 mmol), toluene (3 mL) obtain product 3-butyl-1,3 ( e)-decadiene-5-alkynes-2-base acetic ester (96.8 mg, 88%): liquid.
1H NMR (300 MHz, CDCl 3) δ 5.64 (t, J = 7.5 Hz, 1 H, CH=), 5.02 (d, J = 1.5 Hz, 1 H, one of CH 2=), 4.76 (d, J = 1.5 Hz, 1 H, one of CH 2=), 2.26-2.19 (m, 5 H, CH 2 + CH 3), 2.00 (t, J = 7.2 Hz, 2 H, CH 2), 1.74-1.58 (m, 1 H, CH), 1.49-1.28 (m, 4 H, 2 × CH 2), 0.95-0.88 (m, 9 H, 3 × CH 3); 13C NMR (CDCl 3, 75 MHz) δ 169.1, 153.8, 133.5, 128.1, 100.9, 37.1, 31.0, 28.7, 27.3, 22.9, 22.5, 20.9, 13.9; IR (neat, cm -1) 2957, 2871, 1767, 1642, 1614, 1466, 1368, 1214, 1196, 1145, 1118, 1019; MS (EI) m/z (%) 224 (M +, 2.29), 125 (100); HRMS Calcd for C 14H 24O 2 (M +): 224.1776, Found: 224.1769.
embodiment 4
Press the described method of embodiment 1, different is that substrate used and reagent are: three (triphenyl phosphorus) RHODIUM CHLORIDE (9.7 mg, 0.010 mmol, 1 mol%), triphenyl phosphorus (8.0 mg, 0.031 mmol, 3 mol%), 2-butyl-1-phenyl-2,3-divinyl-1-base acetic ester (242.8 mg, 1 mmol), toluene (6 mL) obtain product 3-butyl-4-phenyl-1,3 ( e)-divinyl-2-base acetic ester.
E- 2e: Liquid; 1H NMR (300 MHz, CDCl 3) δ 7.38-7.31 (m, 2 H, Ar-H), 7.28-7.21 (m, 3 H, Ar-H), 6.69 (s, 1 H, CH=), 5.23 (dd, J = 2.1 and 0.6 Hz, 1 H, one of CH 2=), 4.96 (dd, J = 2.1 and 0.6 Hz, 1 H, one of CH 2=), 2.45-2.37 (m, 2 H, CH 2), 2.25 (s, 3 H, CH 3), 1.66-1.54 (m, 2 H, CH 2), 1.44-1.30 (m, 2 H, CH 2), 0.91 (t, J = 7.2 Hz, 3 H, CH 3); 13C NMR (CDCl 3, 75 MHz) δ 169.0, 153.7, 137.0, 135.6, 128.8, 128.2, 127.2, 127.0, 103.2, 31.3, 27.7, 22.9, 21.0, 13.8; IR (neat, cm -1) 3023, 2958, 2932, 2872, 1764, 1630, 1611, 1492, 1467, 1444, 1369, 1193, 1129, 1074, 1043, 1019; MS (EI) m/z (%) 244 (M +, 2.49), 145 (100); HRMS Calcd for C 16H 20O 2 (M +): 244.1463, Found: 244.1463.
embodiment 5
Press the described method of embodiment 1, different is that substrate used and reagent are: three (triphenyl phosphorus) RHODIUM CHLORIDE (9.4 mg, 0.01 mmol, 1 mol%), triphenyl phosphorus (7.8 mg, 0.03 mmol, 3 mol%), 2-butyl-1-phenyl-2,3-divinyl-1-base p-nitrobenzoic acid ester (342.3 mg, 1 mmol), toluene (6 mL) obtain product 3-butyl-4-phenyl-1,3 ( e)-divinyl-2-base p-nitrobenzoic acid ester (277.4 mg, 81%): solid: m.p. 97.8-98.6 oc (hexane/ethyl acetate).
1H NMR (300 MHz, CDCl 3) δ 8.36 (s, 4 H, Ar-H), 7.37-7.30 (m, 2 H, Ar-H), 7.28-7.20 (m, 3 H, Ar-H), 6.73 (s, 1 H, CH=), 5.37 (d, J = 2.4 Hz, 1 H, one of CH 2=), 5.13 (d, J = 2.4 Hz, 1 H, one of CH 2=), 2.53-2.43 (m, 2 H, CH 2), 1.75-1.60 (m, 2 H, CH 2), 1.48-1.34 (m, 2 H, CH 2), 0.94 (t, J = 7.2 Hz, 3 H, CH 3); 13C NMR (CDCl 3, 75 MHz) δ 162.9, 153.8, 150.8, 136.7, 135.2, 134.9, 131.1, 128.8, 128.3, 127.6, 127.2, 123.7, 103.7, 31.3, 27.8, 22.9, 13.8; IR (KBr, cm -1) 3054, 2958, 2931, 2871, 1743, 1629, 1608, 1529, 1467, 1445, 1349, 1319, 1273, 1235, 1212, 1128, 1092, 1014; MS (EI) m/z (%) 351 (M +, 6.60), 150 (100); Anal. Calcd for C 21H 21NO 4: C 71.78, H 6.02, N 3.99, Found: C 71.98, H 6.07, N 4.01.
embodiment 6
Press the described method of embodiment 1, different is that substrate used and reagent are: three (triphenyl phosphorus) RHODIUM CHLORIDE (4.6 mg, 0.005 mmol, 1 mol%), triphenyl phosphorus (4.1 mg, 0.016 mmol, 3 mol%), 3-butyl-1,2-decadiene-4-base acetic ester (126.5 mg, 0.5 mmol), toluene (3 mL) (eluent:petroleum ether/diethyl ether=60/1) obtain product 3-butyl-1,3 ( e)-decadiene-2-base acetic ester (113.0 mg, 89%): liquid; .
1H NMR (300 MHz, CDCl 3) δ 5.62 (t, J = 7.4 Hz, 1 H, CH=), 5.02 (d, J = 1.8 Hz, 1 H, one of CH 2=), 4.76 (d, J = 1.8 Hz, 1 H, one of CH 2=), 2.26-2.19 (m, 5 H, CH 2 + CH 3), 2.14-2.05 (m, 2 H, CH 2), 1.49-1.22 (m, 12 H, 6 × CH 2), 0.96-0.84 (m, 6 H, 2 × CH 3); 13C NMR (CDCl 3, 75 MHz) δ 169.1, 153.7, 132.9, 129.3, 100.9, 31.7, 31.1, 29.4, 29.1, 28.1, 27.3, 22.9, 22.6, 20.9, 14.0, 13.9; IR (neat, cm -1) 2957, 2928, 2858, 1767, 1642, 1614, 1467, 1368, 1216, 1197, 1141, 1019; MS (EI) m/z (%) 252 (M +, 4.62), 125 (100); HRMS Calcd for C 16H 28O 2 (M +): 252.2089, Found: 252.2090.
embodiment 7
Press the described method of embodiment 1, different is that substrate used and reagent are three (triphenyl phosphorus) RHODIUM CHLORIDE (42.1 mg, 0.046 mmol, 5 mol%), triphenyl phosphorus (38.5 mg, 0.15 mmol, 15 mol%), 2-methyl-3-phenyl-3,4-pentadiene-2-base acetic ester (217.5 mg, 1 mmol), toluene (6 mL) obtain product 4-methyl-3-phenyl-1,3 ( e)-pentadiene-2-base acetic ester (94.3 mg, 43%): liquid.
1H NMR (300 MHz, CDCl 3) δ 7.35-7.22 (m, 3 H, Ar-H), 7.22-7.16 (m, 2 H, Ar-H), 5.03 (s, 1 H, one of CH 2=), 4.81 (s, 1 H, one of CH 2=), 2.06 (s, 3 H, CH 3), 1.92 (s, 3 H, CH 3), 1.66 (s, 3 H, CH 3); 13C NMR (CDCl 3, 75 MHz) δ 168.9, 153.7, 139.8, 136.2, 131.6, 129.6, 128.0, 126.7, 106.0, 22.7, 22.6, 20.7; IR (neat, cm -1) 3056, 3021, 2913, 2857, 1757, 1645, 1492, 1442, 1369, 1236, 1191, 1082, 1019; MS (EI) m/z (%) 216 (M +, 14.25), 131 (100); HRMS Calcd for C 14H 16O 2 (M +): 216.1150, Found: 216.1149.
embodiment 8
Press the described method of embodiment 1, different is that substrate used and reagent are: two (triphenyl phosphorus) carbonyl RHODIUM CHLORIDE (14.0 mg, 0.02 mmol, 2 mol%), 2-allyl group-1-phenyl-2,3-divinyl-1-base acetic ester (228.2 mg, 1 mmol), toluene (6 mL) obtain product 3-α-tolylene-1,5 ( e)-hexadiene-2-base acetic ester (148.6 mg, 65%): liquid.
1H NMR (300 MHz, CDCl 3) δ 7.37-7.22 (m, 5 H, Ar-H), 6.83 (s, 1 H, CH=), 6.07-5.93 (m, 1 H, CH=), 5.28-5.14 (m, 3 H, one of CH 2= + CH 2=), 4.96 (d, J = 1.8 Hz, 1 H, one of CH 2=), 3.24-3.18 (m, 2 H, CH 2), 2.27 (s, 3 H, CH 3); 13C NMR (CDCl 3, 75 MHz) δ 169.0, 153.3, 136.5, 135.5, 131.8, 128.8, 128.7, 128.2, 127.3, 116.5, 104.1, 32.1, 20.9; IR (neat, cm -1) 3080, 3060, 3023, 2979, 2921, 1763, 1631, 1612, 1493, 1443, 1369, 1226, 1189, 1124, 1047, 1020; MS (EI) m/z (%) 228 (M +, 4.15), 145 (100); HRMS Calcd for C 15H 16O 2 (M +): 228.1150, Found: 228.1157.
embodiment 9
Press the described method of embodiment 1, different is that substrate used and reagent are: two (triphenyl phosphorus) carbonyl RHODIUM CHLORIDE (13.7 mg, 0.02 mmol, 2 mol%), 3-phenyl-3,4-pentadiene-2-base acetic ester (201.2 mg, 1 mmol), toluene (6 mL) obtains product 3-phenyl-1,3-( e)-pentadiene-2-base acetic ester (151.5 mg, 75%): liquid.
1H NMR (300 MHz, CDCl 3) δ 7.41-7.27 (m, 3 H, Ar-H), 7.25-7.18 (m, 2 H, Ar-H), 5.98 (q, J = 7.1 Hz, 1 H, CH=), 4.79 (s, 1 H, one of CH 2=), 4.55 (s, 1 H, one of CH 2=), 2.24 (s, 3 H, CH 3), 1.57 (d, J = 7.2 Hz, 3 H, CH 3); 13C NMR (CDCl 3, 75 MHz) δ 169.0, 154.2, 137.0, 136.7, 129.8, 128.2, 127.2, 124.4, 104.6, 20.9, 14.8; IR (neat, cm -1) 3056, 2913, 2856, 1760, 1639, 1615, 1495, 1442, 1370, 1274, 1207, 1180, 1108, 1072, 1019; MS (EI) m/z (%) 202 (M +, 9.93), 160 (100); HRMS Calcd for C 13H 14O 2 (M +): 202.0994, Found: 202.0994.
embodiment 10
Press the described method of embodiment 1, different is that substrate used and reagent are: two (triphenyl phosphorus) carbonyl RHODIUM CHLORIDE (14.0 mg, 0.02 mmol, 2 mol%), 1-p-methoxyphenyl-2-phenyl-2,3-divinyl-1-base acetic ester (292.8 mg, 1 mmol), toluene (6 mL) obtain product 4-p-methoxyphenyl-3-phenyl-1,3 ( e)-divinyl-2-base-1-acetic ester (235.7 mg, 80%) liquid.
1H NMR (300 MHz, CDCl 3) δ 7.42-7.30 (m, 3 H, Ar-H), 7.30-7.24 (m, 2 H, Ar-H), 6.84-6.76 (m, 2 H, Ar-H), 6.70 (s, 1 H, CH=), 6.65-6.58 (m, 2 H, Ar-H), 4.91 (s, 1 H, one of CH 2=), 4.68 (s, 1 H, one of CH 2=), 3.71 (s, 3 H, CH 3), 2.28 (s, 3 H, CH 3); 13C NMR (CDCl 3, 75 MHz) δ 168.9, 158.8, 155.0, 137.7, 134.1, 131.1, 130.1, 128.8, 128.4, 127.7, 126.7, 113.4, 105.7, 55.1, 21.0; IR (neat, cm -1) 3031, 2957, 2935, 2837, 1761, 1603, 1571, 1510, 1463, 1443, 1369, 1303, 1255, 1198, 1167, 1116, 1032; MS (EI) m/z (%) 294 (M +, 44.80), 235 (100); HRMS Calcd for C 19H 18O 3 (M +): 294.1256, Found: 294.1255.
embodiment 11
Press the described method of embodiment 1, different is that substrate used and reagent are: two (triphenyl phosphorus) carbonyl RHODIUM CHLORIDE (14.1 mg, 0.02 mmol, 2 mol%) 1-phenyl-2,3-divinyl-1-base acetic ester (188.5 mg, 1 mmol) toluene (6 mL) obtain product 4-phenyl-1,3 ( e)-divinyl (100.7 mg, 53%): Liquid.
1H NMR (300 MHz, CDCl 3) δ 7.43-7.37 (m, 2 H, Ar-H), 7.37-7.22 (m, 3 H, Ar-H), 6.66 (d, J = 15.9 Hz, 1 H, CH=), 6.59 (d, J = 16.1 Hz, 1 H, CH=), 5.13 (d, J = 1.8 Hz, 1 H, one of CH 2=), 4.98 (d, J = 1.5 Hz, 1 H, one of CH 2=), 2.30 (s, 3 H, CH 3); 13C NMR (CDCl 3, 75 MHz) δ 168.8, 151.8, 135.9, 129.8, 128.6, 128.2, 126.8, 122.5, 106.2, 20.9; IR (neat, cm -1) 3025, 1761, 1642, 1607, 1495, 1449, 1370, 1198, 1075, 1021; MS (EI) m/z (%) 188 (M +, 14.72), 146 (100); HRMS Calcd for C 12H 12O 2 (M +): 188.0837, Found: 188.0835.
embodiment 12
Press the described method of embodiment 1, different is that substrate used and reagent are: two (triphenyl phosphorus) carbonyl RHODIUM CHLORIDE (13.5 mg, 0.02 mmol, 2 mol%) 1-rubigan-2,3-divinyl-1-base acetic ester (217.7 mg, 1 mmol) toluene (6 mL) obtain product 4-rubigan-1,3 ( e)-divinyl-2-base acetic ester (107.4 mg, 49%): liquid.
1H NMR (300 MHz, CDCl 3) δ 7.35-7.25 (m, 4 H, Ar-H), 6.62 (d, J = 16.1 Hz, 1 H, CH=), 6.52 (d, J = 16.1 Hz, 1 H, CH=), 5.14 (d, J = 1.5 Hz, 1 H, one of CH 2=), 5.00 (d, J = 1.8 Hz, 1 H, one of CH 2=), 2.30 (s, 3 H, CH 3); 13C NMR (CDCl 3, 75 MHz) δ 168.7, 151.5, 134.3, 133.8, 128.8, 128.4, 128.0, 123.1, 106.7, 20.9; IR (neat, cm -1) 3040, 1761, 1641, 1609, 1591, 1566, 1490, 1407, 1370, 1299, 1287, 1197, 1091, 1021, 1013; MS (EI) m/z (%) 224 (M ( 37Cl) +, 3.72), 222 (M ( 35Cl) +, 11.03), 145 (100); HRMS Calcd for C 12H 11O 2 35Cl (M +): 222.0448, Found: 222.0448.
embodiment 13
Press the described method of embodiment 1, different is that substrate used and reagent are: two (triphenyl phosphorus) carbonyl RHODIUM CHLORIDE (13.9 mg, 0.02 mmol, 2 mol%) 2-butyl-1-phenyl-2,3-divinyl-1-base carbonic ether (260.3 mg, 1 mmol) toluene (6 mL) obtain product 3-butyl-4-phenyl-1,3 ( e)-divinyl-2-base carbonic ether (199.4 mg, 77%): liquid.
1H NMR (300 MHz, CDCl 3) δ 7.38-7.32 (m, 2 H, Ar-H), 7.29-7.22 (m, 3 H, Ar-H), 6.79 (s, 1 H, CH=), 5.21 (d, J = 2.1 Hz, 1 H, one of CH 2=), 5.07 (d, J = 2.4 Hz, 1 H, one of CH 2=), 3.86 (s, 3 H, CH 3), 2.47-2.37 (m, 2 H, CH 2), 1.67-1.55 (m, 2 H, CH 2), 1.45-1.30 (m, 2 H, CH 2), 0.91 (t, J = 7.2 Hz, 3 H, CH 3); 13C NMR (CDCl 3, 75 MHz) δ 154.1, 153.9, 136.9, 135.2, 128.8, 128.2, 127.4, 127.1, 102.8, 55.3, 31.2, 27.7, 22.9, 13.8; IR (neat, cm -1) 2957, 2872, 1766, 1634, 1612, 1492, 1441, 1275, 1234, 1212, 1134, 1091; MS (EI) m/z (%) 260 (M +, 15.83), 142 (100); HRMS Calcd for C 16H 20O 3 (M +): 260.1412, Found: 260.1412.

Claims (3)

1. one kind synthetic 1, the method of the carboxylicesters of 3 (E)-diene-2-alcohol, it is characterized in that by 2,3-connection enol carboxylicesters 1 occurs 1 under three (triphenylphosphine) RHODIUM CHLORIDE or the catalysis of two (triphenylphosphine) carbonyl RHODIUM CHLORIDE, the rearrangement reaction of 3-ester group, highly selective generates the carboxylicesters 2 of 1,3 (E)-diene-2-alcohol, and reaction formula is as follows:
R 1=alkyl, aryl; R 2=hydrogen, alkyl, aryl or allyl group; R 3=alkyl, aryl or alkoxyl group; The steps include:
(1), 2,3-connection enol carboxylicesters 1 occurs 1 under three (triphenylphosphine) RHODIUM CHLORIDE or the catalysis of two (triphenylphosphine) carbonyl RHODIUM CHLORIDE, the rearrangement reaction of 3-ester group, generate trans 1, the carboxylicesters 2 of 3 (E)-diene-2-alcohol: at a certain temperature, by catalyzer, 2,3-connection enol carboxylicesters 1 adds in reaction flask, the reaction certain hour; (2), after step (1) reacts completely, through concentrated, rapid column chromatography, obtain the carboxylicesters 2 of product 1,3 (E)-diene-2-alcohol.
2. the method for the carboxylicesters of synthetic 1,3 (E) according to claim 1-diene-2-alcohol, is characterized in that the carboxylicesters 2 of described 1,3 (E)-diene-2-alcohol can have phenyl on the 3-position, butyl or allyl group substituting group.
3. the method for the carboxylicesters of synthetic 1,3 (E) according to claim 1-diene-2-alcohol, it is characterized in that described 2,3-connection enol carboxylicesters 1: catalyzer: toluene=1 mmole: 0.01-0.10 mmole: 6 milliliters.
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US3978100A (en) * 1973-04-18 1976-08-31 Kuraray Co., Ltd. Allenic esters, process for preparation thereof and process for rearrangement thereof
CN1724499A (en) * 2005-07-06 2006-01-25 浙江大学 Method of synthesizing beta-halogen-beta, garma, unsaturated aldehyde

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Publication number Priority date Publication date Assignee Title
US3978100A (en) * 1973-04-18 1976-08-31 Kuraray Co., Ltd. Allenic esters, process for preparation thereof and process for rearrangement thereof
CN1724499A (en) * 2005-07-06 2006-01-25 浙江大学 Method of synthesizing beta-halogen-beta, garma, unsaturated aldehyde

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