CN1304346C - Optically active 2,3-dienol and dienol ester and their synthesis and use - Google Patents
Optically active 2,3-dienol and dienol ester and their synthesis and use Download PDFInfo
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- CN1304346C CN1304346C CNB021543690A CN02154369A CN1304346C CN 1304346 C CN1304346 C CN 1304346C CN B021543690 A CNB021543690 A CN B021543690A CN 02154369 A CN02154369 A CN 02154369A CN 1304346 C CN1304346 C CN 1304346C
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Abstract
The present invention relates to an optically active 2, 3-dienol compound and a new environmentally friendly synthesizing method and the application for preparing optically active epoxy compounds, aminoalcohol and furan derivatives thereof. The structural formula of the compound is disclosed in the specification, wherein R<2> is alkyl and alkenyl of C1 to C10, alkynyl and phenyl of C1 to C10, PhCH2CH2, ethyl formate groups and alkoxy or methyl formate groups of C1 to C10, R<1> is alkyl, vinyl and ethynyl of C<1 to 3>, R<3> is H, alkyl of C<1 to 3> and CH2CH2CH2CH2, and R<4> is alkyl and phenyl of C<1 to 3>.
Description
Technical field
The present invention relates to a class optical activity 2,3-connection enol and connection enol ester, synthetic method and purposes, this method is catalyzer with lipase, racemic enol is carried out chiral separation prepare chirality connection enol and connection enol ester.
Background technology
Because optically active 2, the singularity of 3-divinyl-this body structure of 1-alcohol compound has caused this compounds to have the diversity of reaction.Therefore, this compounds is paid attention to by numerous scientist, and becomes the focus of organic chemistry research field.Document J.Am.Chem.Soc., 1990,112,878; Angew.Chem.Int.Ed.1998,37,2392; J.Org.Chem., 1995,60,8130; Tetrahedron lett., 1,996 37,4125; J.Am.Chem.Soc., 1990,112,7434; J.Am.Chem.Soc., 1991,113,6129; In disclose several optically active 2, the synthetic method of 3-divinyl-1-alcohol. as
R=H, PhCH
2CH
2Or cyclohexyl, R '=Me or Et; Document J.Am.Chem.Soc., 1990,112,878; Angew.Chem.Int.Ed.1998,37,2392; J.Org.Chem., 1995,60,8130; Tetrahedron lett., 1,996 37,4125 report 2 of genuine synthesis of optically active, and the characteristics of the method for 3-divinyl-1-alcohol are: 1) utilize the borane reagent of difficult synthetic part diphenyl ethylene diamine to make chiral reagent and aldehyde reaction prepares; 2) utilize organic propargyl tin reagent under the BINOL of chirality catalysis directly and aldehyde reaction prepare; The shortcoming of these methods is: the borane reagent synthetic route of (1) optically active diphenyl ethylene diamine is long, and has used the great toxicity organotin reagent; (2) the great toxicity organotin reagent has directly been used in reaction; (3) reactions steps that has is long; (4) reaction needed anhydrous and oxygen-free condition, operation inconvenience is unfavorable for mass production.In view of this, from environment amenable angle, perhaps the experimental implementation angle is considered, these two kinds of methods are worthless.J.Am.Chem.Soc., 1990,112,7434; J.Am.Chem.Soc., 1991,113,6129 reported method also are to be that catalyzer distich enol splits with Lipase Ak (lipase from Pseudomonas fluorescens), but its substrate has only two, and the ee value of productive rate and ester neither be very high.
Summary of the invention
The purpose of this invention is to provide new optically pure 2 of a class, 3-connection enol and connection enol ester compound.
Another purpose of the present invention provides a kind of above-mentioned optically active 2, the new eco-friendly synthetic method of 3-connection enol and connection enol ester compound.Make 2,3-connection enolization compound obtains more applications.
It is a kind of above-mentioned optically pure 2 that purpose of the present invention also provides, the purposes of 3-connection enol and connection enol ester compound.
Of the present invention optically active 2,3-connection enol and connection enol ester compound, its structural formula is:
Wherein, R
2Be C
1～10Alkyl, C
1～10Thiazolinyl, C
1～C
10Alkynyl, benzyl, ★ PhCH
2CH
2-or C
1～C
10Alkoxyl group; R
1Be C
1-3Alkyl, vinyl, ethynyl; R
3Be H, C
1-3Alkyl; R
4Be C
1～3Alkyl, phenyl;
Perhaps R
2Be ethoxyl methyl, R
1Be ethynyl, R
3Be H and R
4Be methyl.
Compound of the present invention can following structural formula be an example:
It is optically active 2 to the invention provides a synthetic class, the eco-friendly synthetic method of 3-connection enolization compound, and reaction formula is as follows:
Wherein, R
2Be C
1～10Alkyl, C
1～10Thiazolinyl, C
1～C
10Alkynyl, benzyl, ★ PhCH
2CH
2-or C
1～C
10Alkoxyl group; R
1Be C
1～3Alkyl, vinyl, ethynyl; R
3Be H, C
1～3Alkyl; R
4Be C
1～3Alkyl, phenyl;
Perhaps R
2Be ethoxyl methyl, R
1Be ethynyl, R
3Be H and R
4Be methyl.
Optical activity 2 of the present invention, the 3-connection is enols used to utilize different reaction conditionss that Diels-Alder reaction (Diels-Alder) can take place, aldol reaction (aldol), carbonyl allylation reaction (carbonylallylation), thiazolinyl two hydroxylations reaction reactions such as (olefin dihydroxylation).The contriver has been developed the method for utilizing this compounds to prepare optically active epoxy compounds, furan derivative.
Reactions steps of the present invention can specifically describe as follows: in organic solvent, structural formula is
Racemic enol, structural formula be
Acylating reagent under lipase catalysis, obtain optically active 2, the pure and mild enol ester of 3-divinyl-1-, wherein temperature of reaction is 0～80 ℃, the reaction times is 3～168 hours, 10～96 hours recommendation response time.25～60 ℃ of temperature of reaction.The above-mentioned racemic enol and the weight ratio of lipase are 1: 0.05～10, and the mol ratio of racemic enol and acylating reagent is 1: 0.5～50.
Lipase described in the method for the present invention is lipase from candida sp (English name candida antarctica lipaseB, as trade(brand)name Novozym 435), false unicellular lipase (the English name lipase from Pseudomonasfluorescens of fluorescence, as trade(brand)name lipase Ak), cylinder lipase from candida sp (English name lipase from candidacylindracea, as trade(brand)name CCL), porcine pancreatic lipase (English name lipase from pig pancreas, as trade(brand)name PPL), candida rugosa lipase (English name lipase from candida rugosa, trade(brand)name Lipase AY) or false unicellular lipase (English name lipase from Pseudomonas cepacia is as trade(brand)name Lipase PS) etc.Described organic solvent is normal hexane, hexanaphthene, vinyl acetate, methylene dichloride, acetone, ether or isopropyl ether.
A class of the present invention is optically active 2, and the purposes of 3-connection enolization compound can be used for preparing optically active epoxy compounds, amino alcohol or furan derivatives.
The present invention first with lipase to such outer disappear 2,3-divinyl-1-alcohol splits the connection enol and the connection enol ester of preparation chirality, and is simple to operate, is a kind of method easily and effectively.With existing synthesis of optically active 2, the enols used method of 3-connection is compared, and has overcome the drawback of traditional method, has following characteristics: (1) has used conventional common organic reagent, has avoided the great toxicity organotin reagent.(2) reaction need not anhydrous and oxygen-free, and is simple to operate, convenient post-treatment.(3) conversion unit is simple, is easy to suitability for industrialized production.
Embodiment
Following examples help to understand the present invention, but are not limited to content of the present invention:
Embodiment 1
(S)-1-methyl-2-butyl-2,3-divinyl-1-pure and mild (R)-acetate-1-methyl-2-butyl-2,3-divinyl-1-alcohol ester is got the round-bottomed flask of a 25ml, (trade(brand)name Novozym 435 to add the 70mg lipase from candida sp, English name candida antarctica lipase B) or false unicellular lipase (the trade(brand)name lipase Ak of fluorescence, English name lipasefrom Pseudomonas fluorescens), 5ml vinyl acetate and 0～5ml normal hexane, 1-methyl-2-butyl-2 that 100mg disappears outward, 3-divinyl-1-alcohol, the sealing of jumping a queue was reacted 96 hours down in 30 ℃, filter, the ether detersive enzyme adds an amount of column chromatography silica gel, and decompression is spin-dried for into solid, cross post (sherwood oil: ethyl acetate=10: 1), get product.(S)-and 1-methyl-2-butyl-2,3-divinyl-1-alcohol 39mg, y:39%, ee:99.0% and (R)-acetate-1-methyl-2-butyl-2,3-divinyl-1-alcohol ester 40mg, y:30.7%, ee:98.9%
(S)-and 1-methyl-2-butyl-2,3-divinyl-1-alcohol:
1H?NMR(300MHz，CDCl
3)δ4.82-4.78(m，2H)，4.20-4.02(m，1H)，2.02-1.80(m，2H)，1.60(s，1H)，1.50-1.05(m，7H)，0.82(t，J＝6.7Hz，3H)；
13C?NMR(75.40MHz，CDCl
3)δ203.72，108.67，78.50，76.57，67.58，29.69，27.53，22.37，21.89，13.84；MS(m/e)140(M
+，2.31)；IR(neat)3331.7cm
-1?1956.0cm
-1；
(R)-and acetate-1-methyl-2-butyl-2,3-divinyl-1-alcohol ester:
1H NMR (300MHz, CDCl
3) δ 5.32-5.20 (m, 1H), 4.80-4.75 (m, 2H), 1.97 (s, 3H), 1.49-1.00 (m, 9H), 0.81 (t, J=6.7Hz, 3H);
13C NMR (75.40MHz, CDCl
3) δ 205.96,170.69,105.03,78.36,70.47,29.81,28.25,22.55,21.44,19.08,14.10; MS (m/e) 183 (M+1
+, 100); IR (neat) 1958.1cm
-1, 1739.0cm
-1HRMS (M
+-COCH
3), C
9H
15O: calculated value: 139.1123, measured value: 139.1130.
Embodiment 2
(S)-1-methyl-2-propyl group-2,3-divinyl-1-pure and mild (R)-acetate-1-methyl-2-propyl group-2,3-divinyl-1-alcohol ester is got the round-bottomed flask of a 25ml, add 50～70mg porcine pancreatic lipase (trade(brand)name PPL, English name lipasefrom pig pancreas) enzyme or lipase from candida sp, 5ml vinyl acetate and 0-10ml methylene dichloride, 1-methyl-2-propyl group-2 that 100mg disappears outward, 3-divinyl-1-alcohol, the sealing of jumping a queue was reacted 102 hours down in 30 ℃, filter, the ether detersive enzyme adds an amount of column chromatography silica gel, and decompression is spin-dried for into solid, cross post (sherwood oil: ethyl acetate=10: 1), get product (S)-1-methyl-2-propyl group-2,3-divinyl-1-alcohol 36mg, y:36%, ee:99.7% and (R)-acetate-1-methyl-2-propyl group-2,3-divinyl-1-alcohol ester 48mg, y:36.4%, y:95.4
(S)-and 1-methyl-2-propyl group-2,3-divinyl-1-alcohol:
1H?NMR(300MHz，CDCl
3)δ4.93-4.80(m，2H)，4.29-4.13(m，1H)，2.09-1.84(m，2H)，1.68(s，1H)，1.57-1.40(m，2H)，1.30(d，J＝6.7，3H)，0.93(t，J＝7.3，3H)；
13C?NMR(75.40MHz，CDCl
3)δ203.66，108.75，78.90，67.70，30.17，22.07，20.88，13.89；MS(m/z)126(M
+，0.9)；IR(neat)3349.8cm
-1，1955.4cm
-1；
(R)-and acetate-1-methyl-2-propyl group-2,3-divinyl-1-alcohol ester:
1H?NMR(300MHz，CDCl
3)δ5.38-5.22(m，1H)，4.93-4.80(m，2H)，2.04(s，3H)，2.00-1.80(m，2H)，1.58-1.36(m，4H)，1.32(d，J＝5.7Hz，3H)，0.91(t，J＝7.3，3H)；
13CNMR(75.40MHz，CDCl
3)δ206.03，170.87，104.89，78.42，70.55，30.72，21.53，20.95，19.14，14.07；MS(m/e)126(M
++1-COCH
3，25.46)；IR(neat)1957.9cm
-1，1738.1cm
-1。
Embodiment 3
(S)-1-methyl-2-amyl group-2,3-divinyl-1-pure and mild (R)-acetate-1-methyl-2-amyl group-2,3-divinyl-1-alcohol ester is got the round-bottomed flask of a 25ml, add 70mg lipase from candida sp or false unicellular lipase (trade(brand)name Lipase PS, English name lipase from Pseudomonas cepacia), the 5ml vinyl acetate, 1-methyl-2-amyl group-2 that 100mg disappears outward, 3-divinyl-1-alcohol, the sealing of jumping a queue was reacted 102 hours down in 30 ℃, filter, the ether detersive enzyme adds an amount of column chromatography silica gel, and decompression is spin-dried for into solid, cross post (sherwood oil: ethyl acetate=10: 1), get product (S)-1-methyl-2-amyl group-2,3-divinyl-1-alcohol 40.0mg, y:40%, ee:99.5% and (R)-acetate-1-methyl-2-amyl group-2,3-divinyl-1-alcohol ester 49mg, y:38.9%, ee:99%
(S)-and 1-methyl-2-amyl group-2,3-divinyl-1-alcohol:
1H NMR (300MHz, CDCl
3) δ 4.93-4.80 (m, 2H), 4.27-4.07 (M, 1H), 2.13-1.87 (m, 2H), 1.68 (s, 1H), 1.60-1.11 (m, 9H), 1.25 (d, J=6.6Hz, 3H), 0.88 (t, J=6.7Hz, 3H);
13C NMR (75.40MHz, CDCl
3) δ 204.27,108.81,78.36,67.82,31.79,27.98,27.48,22.67,22.07,14.16; APCI MS (m/e) 155 (M+1
+); IR (neat) 3346.0cm
-1, 1955.5cm
-1HRMS (M
++ 1), C
10H
19O: calculated value: 155.1436, measured value: 155.1436;
(R)-and acetate-1-methyl-2-amyl group-2,3-divinyl-1-alcohol ester:
1H NMR (300MHz, CDCl
3) δ 5.32-5.20 (m, 1H), 4.80-4.75 (m, 2H), 1.98 (s, 3H), 1.98-1.80 (m, 2H), 1.49-1.00 (m, 9H), 0.84 (t, J=6.7Hz, 3H);
13C NMR (75.4MHz, CDCl
3) δ 205.99,170.72,105.82,78.38,70.49,31.70,28.53,27.34,22.69,21.44,19.09,14.25; APCIMS (m/e) 197 (M+1
+); IR (neat) 1958cm
-1, 1739cm
-1HRMS (M-COCH
3), C
10H
17O: calculated value: 153.1279, measured value: 153.12691.
Embodiment 4
(S)-and 1-methyl-2-hexyl-2,3-divinyl-1-pure and mild (R)-acetate-1-methyl-2-hexyl-2,3-divinyl-1-alcohol ester
Get the round-bottomed flask of a 25ml, add false unicellular lipase (the trade(brand)name lipase Ak of 40～80mg lipase from candida sp or fluorescence, English name lipase from Pseudomonas fluorescens), 5ml vinyl acetate and 0～5ml isopropyl ether, 1-methyl-2-hexyl-2 that 100mg disappears outward, 3-divinyl-1-alcohol, the sealing of jumping a queue was reacted 102 hours down in 30 ℃, filter, the ether detersive enzyme adds an amount of column chromatography silica gel, and decompression is spin-dried for into solid, cross post (sherwood oil: ethyl acetate=10: 1), get product (S)-1-methyl-2-hexyl-2,3-divinyl-1-alcohol 31mg, y:31%, 99.1% and (R)-acetate-1-methyl-2-hexyl-2,3-divinyl-1-alcohol ester 50mg, y:40%, ee:99.1%
(S)-and 1-methyl-2-hexyl-2,3-divinyl-1-alcohol:
1H NMR (300MHz, CDCl
3) δ 4.96-4.80 (m, 2H), 4.33-4.09 (m, 1H), 2.13-1.83 (m, 2H), 1.65 (s, 1H), 1.57-1.04 (m, 11H), 0.87 (t, J=6.7Hz, 3H);
13C NMR (75.40MHz, CDCl
3) δ 203.64,108.83,78.71,67.62,31.62,28.98,27.93,27.52,22.54,21.96,13.98; APCI MS (m/e) 169 (M
++ 1); IR (neat) 3339cm
-1, 1956cm
-1HRMS (M+1), C
11H
21O: calculated value: 169.1592, measured value: 169.1596;
(R)-and acetate-1-methyl-2-hexyl-2,3-divinyl-1-alcohol ester:
1H NMR (300MHz, CDCl
3) δ 5.37-5.20 (m, 1H), 4.89-4.71 (m, 2H), 1.98 (s, 3H), 1.97-1.80 (m, 2H), 1.44-1.09 (m, 11H), 0.81 (t, J=7.3Hz, 3H);
13C NMR (75.40MHz, CDCl
3) δ 204.76,169.59,103.87,77.20,69.33,30.65,27.94,27.37,26.41,21.60,20.28,17.89,13.07; APCI MS (m/e) 211 (M
++ 1); IR (neat) 1958cm
-1, 1940cm
-1HRMS (M
+-COCH
3), C
11H
19O: calculated value: 167.1434, measured value: 167.1441.
Embodiment 5
(S)-and 1-methyl-2-heptyl-2,3-divinyl-1-pure and mild (R)-acetate-1-methyl-2-heptyl-2,3-divinyl-1-alcohol ester
Get the round-bottomed flask of a 25ml, add enzyme as described in the embodiment 1,1-methyl-2-heptyl-2 that 5ml vinyl acetate, 100mg disappear outward, 3-divinyl-1-alcohol, the sealing of jumping a queue, reacted 102 hours down in 30 ℃, filter the ether detersive enzyme, add an amount of column chromatography silica gel, decompression is spin-dried for into solid, crosses post (sherwood oil: ethyl acetate=10: 1), get product (S)-1-methyl-2-heptyl-2,3-divinyl-1-alcohol 45mg, y:45%, ee:99% and (R)-acetate-1-methyl-2-heptyl-2,3-divinyl-1-alcohol ester 60mg, y:48.8%, ee:99%
(S)-and 1-methyl-2-heptyl-2,3-divinyl-1-alcohol:
1H NMR (300MHz, CDCl
3) δ 4.89-4.76 (m, 2H), 4.20-4.00 (m, 1H), 2.09-1.78 (m, 2H), 1.63 (s, 1H), 1.53-1.00 (m, 13H), 0.78 (t, J=6.1Hz, 3H);
13C NMR (75.40MHz, CDCl
3) δ 204.18,108.94,78.58,67.87,30.03,29.56,29.37,28.11,27.85,22.14,14.21; APCI MS (m/e) 183 (M
++ 1); IR (neat) 3341cm
-1, 1956cm
-1HRMS (M+1), C
12H
23O: calculated value: 183.1749, measured value: 183.1749;
(R)-and acetate-1-methyl-2-heptyl-2,3-divinyl-1-alcohol ester:
1H NMR (300MHz, CDCl
3) δ 5.37-5.16 (m, 1H), 4.89-4.64 (m, 2H), 1.98 (s, 3H), 1.96-1.84 (m, 2H), 1.53-1.04 (m, 13H), 0.81 J=6.10Hz, 3H);
13C NMR (75.40MHz, CDCl
3) δ 204.76,169.58,103.87,77.19,69.32,30.81,28.25,28.11,27.37,26.46,21.63,20.28,17.89,13.08; APCI MS (m/e) 225.2 (M
++ 1); IR (neat) 1958cm
-11739cm
-1HRMS (M
++ 1-COCH
3), C
12H
22O: calculated value: 182.1671, measured value: 182.1680.
Embodiment 6
(S)-and 1-methyl-2-phenmethyl-2,3-divinyl-1-pure and mild (R)-acetate-1-methyl-2-phenmethyl-2,3-divinyl-1-alcohol ester
Get the round-bottomed flask of a 25m1, add enzyme such as embodiment 2,1-methyl-2-benzyl-2 that 5ml vinyl acetate, 100mg disappear outward, 3-divinyl-1-alcohol, the sealing of jumping a queue, reacted 102 hours down in 30 ℃, filter the ether detersive enzyme, add an amount of column chromatography silica gel, decompression is spin-dried for into solid, crosses post (sherwood oil: ethyl acetate=10: 1), get product (S)-1-methyl-2-benzyl-2,3-divinyl-1-alcohol 42mg, y:42%, ee:96.8% and (R)-acetate-1-methyl-2-benzyl-2,3-divinyl-1-alcohol ester 54mg, y:44%, ee:99.2%
(S)-and 1-methyl-2-phenmethyl-2,3-divinyl-1-alcohol:
1H?NMR(300MHz，CDCl
3)δ7.36-7.12(m，5H)，4.84-4.80(m，2H)，4.24-4.16(m，1H)，3.50-3.30(m，2H)，1.60(s，1H)，1.20(d，J＝6.7Hz?3H)；
13C?NMR(75.40MHz，CDCl
3)δ；205.59，139.76，129.33，128.58，126.56，108.33，78.40，67.19，35.97，22.40；MS(m/e)174(M
+，0.12)；IR(neat)3362.5cm
-1，1956.3cm
-1；
(R)-and acetate-1-methyl-2-phenmethyl-2,3-divinyl-1-alcohol ester:
1H NMR (300MHz, CDCl
3) δ 7.37-7.09 (m, 5H), 5.36-5.24 (m, 1H), 4.89-4.80 (m, 2H), 3.40-3.27 (m, 2H), 2.03 (s, 3H), 1.30 (d, J=6.7,3H);
13C NMR (75.40MHz, CDCl
3) δ 207.25,170.74,139.23,129.16,128.49,126.54,104.52,78.3l, 69.93,36.45,2l.37,19.22; MS (m/e) 217 (M+1
+); IR (neat) 1958.4cm
-1, 1736.6cm
-1Ultimate analysis, calculated value: C:77.78%, H:7.400 measured value: 77.75%, 7.30%.
Embodiment 7
(S)-and 1-methyl-2-styroyl-2,3-divinyl-1-pure and mild (R)-acetate-1-methyl-2-styroyl-2,3-divinyl-1-alcohol ester
Get the round-bottomed flask of a 25ml, add enzyme such as embodiment 3, the 5ml vinyl acetate, the 1-methyl that 100mg disappears outward-2-styroyl base-2,3-divinyl-1-alcohol, the sealing of jumping a queue, reacted 102 hours down in 30 ℃, filter the ether detersive enzyme, add an amount of column chromatography silica gel, decompression is spin-dried for into solid, crosses post (sherwood oil: ethyl acetate=10: 1), get product (S)-1-methyl-2-styroyl-2,3-divinyl-1-alcohol 50mg, y:50%, ee:98.6%; (R)-and acetate-l-methyl-2-styroyl-2,3-divinyl-1-alcohol ester 54mg, y:44%, ee:94.3%
(S)-and 1-methyl-2-styroyl-2,3-divinyl-1-alcohol:
1H NMR (300MHz, CDCl
3) δ 7.44-7.04 (m, 5H), 5.00-4.80 (m, 2H), 4.33-4.09 (m, 1H), 2.79 (t, J=7.32H), 2.40-2.22 (m, 2H), 1.84 (s, 1H), 1.32 (d, J=3.7Hz);
13C NMR (75.40MHz, CDCl
3) 6 203.95,141.9l, 128.38,128.38,128.25 125.83,108.24,79.33,67.83,33.95,29.63,21.95; APCI MS (m/e) (M
++ 1); IR (neat) 3363cm
-1, 1955cm
-1HRMS (M
++ 1), C
13H
17O: calculated value: 189.1279, measured value: 189.1280;
(R)-and acetate-1-methyl-2-styroyl-2,3-divinyl-1-alcohol ester
:
1H NMR (300MHz, CDCl
3) δ 7.42-7.04 (m, 5H), 5.44-5.24 (m, 1H), 4.96-4.84 (m, 2H), 2.74 (t, J=7.9Hz, 2H), 2.40-2.11 (m, 2H), 2.03 (s, 3H), 1.34 (d, J=6.1Hz);
13C NMR (75.40MHz, CDCl
3) δ 205.72,170.28,141.68,128.68,128.16,125.75,104.30,78.72,7012,33.71,29.98,21.07,18.74; APCI MS (m/e) 231 (M
++ 1); IR (neat) 1958cm
-1, 1737cm
-1HRMS (M
++ 1-COCH
3), C
L3H
15O: calculated value: 187.1123, measured value: 187.1118.
Embodiment 8
(S)-and 1-methyl-2 allyl group-2,3-divinyl-1-pure and mild (R)-acetate-1-methyl-2-allyl group-2,3-divinyl-1-alcohol ester
Get the round-bottomed flask of a 25ml, add enzyme such as embodiment 1, the 1-methyl that 5ml vinyl acetate, 100mg disappear outward-2-allyl group base-2,3-divinyl-1-alcohol, the sealing of jumping a queue, reacted 102 hours down in 30 ℃, filter the ether detersive enzyme, add an amount of column chromatography silica gel, decompression is spin-dried for into solid, crosses post (sherwood oil: ethyl acetate=10: 1), get product (S)-1-methyl-2 allyl group-2,3-divinyl-1-alcohol 31mg, y:31%, ee:99.7% and (R)-acetate-1-methyl-2-allyl group-2,3-divinyl-1-alcohol ester 51mg, y:38%, ee:98.8%
(S)-and 1-methyl-2 allyl group-2,3-divinyl-1-alcohol:
1H NMR (300MHz, CDCl
3) δ 5.84-5.64 (m, 1H), 5.09-4.96 (m, 2H), 4.84-4.76 (m, 2H), 4.29-4.04 (m, 2H), 2.84-2.60 (m, 2H), 1.57 (s, 1H), 1.23 (d, J=6.7Hz, 3H);
13C NMR (75.40MHz, CDCl
3) δ 204.70,135.90,116.24,107.01,78.63,67.61,33.34,22.10; MS (m/e) 124 (M
+, 0.65); IR (neat) 3342cm
-1, 1957cm
-1HRMS (M
+-OH), C
8H
12O: calculated value: 107.0861, measured value: 107.0856.
(R)-and acetate-1-methyl-2-allyl group-2,3-divinyl-1-alcohol ester:
1H NMR (300MHz, CDCl
3) δ 5.89-5.67 (m, 1H), 5.40-5.23 (m, 1H), 5.10-5.00 (m, 2H), 4.91-4.78 (m, 2H), 2.84-2.63 (m, 2H), 2.05 (s, 3H), 1.32 (d, J=6.1Hz, 3H);
13C NMR (75.40MHz, CDCl
3) δ 206.06,170.55,135.08,116.17,103.10,78.31,69.77,33.53,21.18,18.74; APCI MS (m/e) 167 (M
++ 1); IR (neat) 1959cm
-1, 1738cm
-1HRMS (M-COCH
3), C
8H
12O: calculated value: 124.0889, measured value: 124.0864.
Embodiment 9
(S)-and 1-ethyl-2-butyl-2,3-divinyl-1-pure and mild (R)-acetate-1-ethyl-2-butyl-2,3-divinyl-1-alcohol ester
Get the round-bottomed flask of a 25ml, add enzyme such as embodiment 1,1-ethyl-2-butyl-2 that 5ml vinyl acetate, 100mg disappear outward, 3-divinyl-1-alcohol, the sealing of jumping a queue, reacted 102 hours down in 30 ℃, filter the ether detersive enzyme, add an amount of column chromatography silica gel, decompression is spin-dried for into solid, crosses post (sherwood oil: ethyl acetate=10: 1), get product (S)-1-ethyl-2-butyl-2,3-divinyl-1-alcohol 48mg, y:48%, ee:99.0% and (R)-acetate-1-ethyl-2-butyl-2,3-divinyl-1-alcohol ester 54mg, y:43%, ee:99.5%
(S)-and 1-ethyl-2-butyl-2,3-divinyl-1-alcohol:
1H NMR (300MHz, CDCl
3) δ 4.93-4.76 (m, 2H), 4.04-3.99 (m, 1H), 2.09-1.80 (m, 2H), 1.80-1.16 (m, 6H), 1.00-0.71 (m, 6H);
13C NMR (75.4MHz, CDCl
3) δ 204.64,107.52,78.70,73.38,30.04,28.54,27.76,22.72,14.17,9.92; APCI MS (m/e) 155 (M
++ 1); IR (neat) 3342cm
-1, 1956cm
-1HRMS (M
++ 1), C
10H
19O: calculated value: 155.1436, measured value: 155.1431.
(R)-and acetate-1-ethyl-2-butyl-2,3-divinyl-1-alcohol ester:
1H NMR (300MHz, CDCl
3) δ 5.20-5.04 (m, 1H), 4.93-4.68 (m, 2H), 2.04 (s, 3H), 2.00-1.80 (m, 2H), 1.76-1.64 (m, 2H), 1.49-1.20 (m, 4H), 1.00-0.71 (m, 6H);
13C NMR (75.40MHz, CDCl
3) δ 206.33,170.75,103.50,77.89,75.56,29.80,28.00,26.08,22.55,21.31,14.08,10.05; APCI MS (m/e) 197 (M
++ 1); IR (neat) 1958cm
-1, 1740cm
-1HRMS (M-COCH
3), C
10H
18O: calculated value: 154.1357, measured value: 154.1346.
Embodiment 10
(S)-and 1-ethyl-2-propyl group-2,3-divinyl-1-pure and mild (R)-acetate-1-ethyl-2-propyl group-2,3-divinyl-1-alcohol ester
Get the round-bottomed flask of a 25ml, add enzyme such as embodiment 1,1-ethyl-2-propyl group-2 that 5ml vinyl acetate, 100mg disappear outward, 3-divinyl-1-alcohol, the sealing of jumping a queue, reacted 102 hours down in 30 ℃, filter the ether detersive enzyme, add an amount of column chromatography silica gel, decompression is spin-dried for into solid, crosses post (sherwood oil: ethyl acetate=10: 1), get product (S)-1-ethyl-2-propyl group-2,3-divinyl-1-alcohol 44mg, y:44%, ee:96.3% and (R)-acetate-1-ethyl-2-propyl group-2,3-divinyl-1-alcohol ester 48mg, (y:37.%, ee:99.7%).
(S)-and 1-ethyl-2-propyl group-2,3-divinyl-1-alcohol:
1H?NMR(300MHz，CDCl
3)δ4.96-4.74(m，2H)，4.00-3.82(m，1H)，2.02-1.80(m，2H)，1.80-1.24(m，5H)，1.02-0.80(m，6H)；
13C?NMR(75.40MHz，CDCl
3)δ204.64，107.30，78.63，73.36，30.15，28.52，21.08，14.14，9.91；MS(m/e)140(M
+，3.81)；IR(neat)3361cm
-1，1955cm
-1；
(R)-and acetate-1-ethyl-2-propyl group-2,3-divinyl-1-alcohol ester:
1H NMR (300MHz, CDCl
3) δ 5.19-5.06 (m, 1H), 4.89-4.63 (m, 2H), 2.02 (s, 3H), 1.97-1.74 (m, 2H), 1.74-1.52 (m, 2H), 1.41 (q, J=7.2Hz, 2H), 1.00-0.70 (m, 6H);
13CNMR (75.40MHz, CDCl
3) δ 206.02,170.49,103.01,77.61,75.25,30.1l, 25.77,21.06,20.59,13.73,9.79; MS (m/e) 140 (M
++ 1-COCH
3, 2.83); IR (neat) 1958cm
-1, 1940cm
-1HRMS (M
++ 1-COCH
3), C
9H
16O, calculated value: 140.1201, measured value: 140.1192.
Embodiment 11
(S)-and 1-ethyl-2-amyl group-2,3-divinyl-1-pure and mild (R)-acetate-1-ethyl-2-amyl group-2,3-divinyl-1-alcohol ester
Get the round-bottomed flask of a 25ml, add enzyme such as embodiment 1, the 5ml vinyl acetate, 1-ethyl-2-amyl group-2 that 100mg disappears outward, 3-divinyl-1-alcohol, the sealing of jumping a queue, reacted 102 hours down in 30 ℃, filter, the ether detersive enzyme adds an amount of column chromatography silica gel, decompression is spin-dried for into solid, cross post (sherwood oil: ethyl acetate=10: 1), get product (S)-1-ethyl-2-amyl group-2,3-divinyl-1-alcohol 39mg, y:39%, ee:99.4% and (R)-acetate-1-ethyl-2-amyl group-2, and 3-divinyl-1-alcohol ester 49mg (y:38.8%, ee:99.5%)
(S)-and 1-ethyl-2-amyl group-2,3-divinyl-1-alcohol:
1H?NMR(300MHz，CDCl
3)δ5.00-4.76(m，2H)，4.04-3.80(m，1H)，2.04-1.80(m，2H)，1.80-1.08(m，9H)，1.08-0.80(m，6H)；
13C?NMR(75.40MHz，CDCl
3)δ204.36，107.19，78.28，73.11，31.56，28.23，27.65，27.24，22.46，13.99，9.64；MS(m/e)168(M
+，1.60)；IR(neat)3355cm
-1，1955cm
-1.
(R)-and acetate-1-ethyl-2-amyl group-2,3-divinyl-1-alcohol ester:
1H NMR (300MHz, CDCl
3) δ 5.03-4.97 (m, 1H), 4.74-4.57 (m, 2H), 1.93 (s, 3H), 1.91-1.79 (m, 2H), 1.75-1.50 (m, 2H), 1.47-1.00 (m .7H), 0.96-0.59 (m, 6H);
13C NMR (75.40MHz, CDCl
3) δ 206.03,170.48,103.26,77.67,75.29,31.43,27.99,27.05,25.81,22.42,21.07,13.98,9.81; MS (m/e) 168 (M
++ 1-COCH
3, 1.75); IR (neat) 1958cm
-1, 1940cm
-1HRMS (M
++ 1-COCH
3): C
11H
20O, calculated value: 168.1514, measured value: 168.1497.
Embodiment 12
(S)-and 1-ethyl-2-heptyl-2,3-divinyl-1-pure and mild (R)-acetate-1-ethyl-2-heptyl-2,3-divinyl-1-alcohol ester
Get the round-bottomed flask of a 25ml, add enzyme such as embodiment 3, the 5ml vinyl acetate, 1-ethyl-2-heptyl-2 that 100mg disappears outward, 3-divinyl-1-alcohol, the sealing of jumping a queue was reacted 102 hours down in 30 ℃, filter, the ether detersive enzyme adds an amount of column chromatography silica gel, and decompression is spin-dried for into solid, cross post (sherwood oil: ethyl acetate=10: 1), get product.Product (S)-1-ethyl-2-heptyl-2,3-divinyl-1-alcohol 49mg (y:49%, ee:99.4%) and (R)-acetate-l-ethyl-2-heptyl-2,3-divinyl-1-alcohol ester 57mg (y:46.8%, ee:99.3%)
(S)-and 1-ethyl-2-heptyl-2,3-divinyl-1-pure and mild (R)-acetate-1-ethyl-2-heptyl-2,3-divinyl-1-alcohol ester is got the round-bottomed flask of a 25ml, add the 70mg enzyme, 1-ethyl-2-heptyl-2 that 5ml vinyl acetate, 100mg disappear outward, 3-divinyl-1-alcohol, the sealing of jumping a queue was reacted 102 hours down in 30 ℃, filter, the ether detersive enzyme adds an amount of column chromatography silica gel, and decompression is spin-dried for into solid, cross post (sherwood oil: ethyl acetate=10: 1), get product.
(S)-and 1-ethyl-2-heptyl-2,3-divinyl-1-alcohol:
1H NMR (300MHz, CDCl
3) δ 5.00-4.67 (m, 2H), 4.09-3.80 (m, 1H), 2.13-1.80 (s, 2H), 1.80-1.00 (m, 13H), 1.00-0.80 (m, 6H);
13C NMR (75.40MHz, CDCl
3) δ 204.32,107.34,78.57,73.10,31.82,29.36,29.16,28.30,27.84,27.63,22.63,14.09,9.67; MS (m/e) 196 (M
+, 4.55); IR (neat) 3344cm
-1, 1955cm
-1HRMS, C
13H
24O, calculated value: 196.1827, measured value: 196.1849;
(R)-and acetate-1-ethyl-2-heptyl-2,3-divinyl-1-alcohol ester:
1H NMR (300MHz, CDCl
3) δ 5.20-5.12 (m, 1H), 4.86-4.65 (m, 2H), 2.05 (s, 3H), 1.97-1.83 (m, 2H), 1.80-1.57 (m, 2H), 1.51-1.07 (m, 10H), 0.96-0.74 (m, 6H);
13C NMR (75.40MHz, CDCl
3) δ 206.05,170.56,103.29,77.71,75.34,31.80,29.23,29.11,28.06,27.41,25.84,22.62,21.13,14.05,9.86; MS (m/e) 196 (M
++ 1-COCH
3, 13.84); IR (neat) 3344cm
-1, 1955cm
-1HRMS (M
++ 1-COCH
3), C
13H
24O, calculated value: 196.1827, measured value: 196.1781.
Embodiment 13
(S)-and 1-vinyl-2-butyl-2,3-divinyl-1-pure and mild (R)-acetate-1-vinyl-2-butyl-2,3-divinyl-1-alcohol ester
Get the round-bottomed flask of a 25ml, add 70mg enzyme such as embodiment 3, the 5ml vinyl acetate, 1-vinyl-2-butyl-2 that 100mg disappears outward, 3-divinyl-1-alcohol, the sealing of jumping a queue was reacted 102 hours down in 30 ℃, filter, the ether detersive enzyme adds an amount of column chromatography silica gel, and decompression is spin-dried for into solid, cross post (sherwood oil: ethyl acetate=10: 1), product (S)-1-vinyl-2-butyl-2,3-divinyl-1-alcohol 50 (97.8%, y:50%) and (R)-acetate-1-vinyl-2-butyl-2,3-divinyl-1-alcohol ester 59mg (ee:98.9%, y:46%).
(S)-and 1-vinyl-2-butyl-2,3-divinyl-1-alcohol: liquid;
1H NMR (300MHz, CDCl
3) δ 5.95-5.78 (m, 1H), 5.29-5.20 (m, 1H), 5.20-5.12 (m, 1H), 4.92-4.86 (m, 2H), 4.50-4.40 (m, 1H), 2.09 (s, 1H), 2.00-1.88 (m, 2H), 1.50-1.20 (m, 4H), 0.88 (t, J=7.2Hz, 3H);
13C NMR (75.4MHz, CDCl
3) δ 204.06,138.68,115.53,106.80,79.22,72.94,29.62,27.57,22.33,13.84; MS (m/z) 152 (M
+, 0.21); IR (neat) 3367.3,1956.2cm
-1HRMS (M
+), C
10H
16O, calculated value: 152.1201, measured value: 152.1222.
(R)-and acetate-1-vinyl-2-butyl-2,3-divinyl-1-alcohol ester: liquid;
1H NMR (300MHz, CDCl
3) δ 5.88-5.78 (m, 1H), 5.64-5.58 (m, 1H), 5.30-5.17 (m, 2H), 4.84-4.78 (m, 2H), 2.06 (s, 3H);
13C NMR (75.40MHz, CDCl
3) δ 206.11,169.94,134.59,117.21,102.98,78.14,74.64,29.47,27.71,22.26,21.08,13.83; MS (m/e) 151 (M
+-COCH
3, 3.01); HRMS (M
+-COCH
3), C
10H
15O, calculated value: 151.1123, measured value: 151.1120
Embodiment 14
(S)-and 1-vinyl-2-allyl group-2,3-divinyl-1-pure and mild (R)-acetate-1-vinyl-2-allyl group-2,3-divinyl-1-alcohol ester
Get-round-bottomed flask of individual 25ml, add 70mg enzyme such as embodiment 4, the 5ml vinyl acetate, 1-vinyl-2-allyl group-2 that 100mg disappears outward, 3-divinyl-1-alcohol, the sealing of jumping a queue was reacted 102 hours down in 30 ℃, filter, the ether detersive enzyme adds an amount of column chromatography silica gel, and decompression is spin-dried for into solid, cross post (sherwood oil: ethyl acetate=10: 1), product (S)-1-vinyl-2-allyl group-2,3-divinyl-1-alcohol 39mg (ee:99.9%, y:39%) and (R)-acetate-1-vinyl-2-allyl group-2,3-divinyl-1-alcohol ester 60mg (ee:98.3%, y:46%).
(S)-and 1-vinyl-2-allyl group-2,3-divinyl-1-alcohol: liquid;
1H NMR (300MHz, CDCl
3) δ 5.95-5.78 (m, 2H), 5.32-5.00 (m, 4H), 4.53-4.48 (m, 1H), 2.78-2.62 (m, 2H), 2.17 (s, 1H); MS (m/z) 136 (M
+, 2.35); IR (neat) 3378.5,1957.0cm
-1HRMS (M
+), C
9H
12O, calculated value: 136.0888, measured value: 136.0864.
(R)-and acetate-1-vinyl-2-allyl group-2,3-divinyl-1-alcohol ester:
1H NMR (300MHz, CDCl
3)
1H NMR (300MHz, CDCl
3) δ 5.84-5.75 (m, 2H), 5.75-5.64 (m, 2H), 5.32-5.26 (m, 2H), 5.20-4.98 (m, 2H), 4.82-4.78 (m, 2H), 2.78-2.72 (m, 2H), 2.08 (s, 3H);
13C NMR (75.40MHz, CDCl
3) δ 206.80,170.13,135.21,134.59,117.74,116.58,101.66,78.58,74.39,33.45,21.34; MS (m/e) 135 (M
+COCH
3, 10.48); HRMS (M
+-COCH
3): Calcd for C
9H
11O:135.0810, found:135.0789
Embodiment 15
(S)-and 1-ethynyl-2-butyl-2,3-divinyl-1-pure and mild (R)-acetate-1-ethynyl-2-butyl-2,3-divinyl-1-alcohol ester
Get the round-bottomed flask of a 25ml, add 70mg enzyme such as embodiment 1, the 5ml vinyl acetate, 1-ethynyl-2-butyl-2 that 100mg disappears outward, 3-divinyl-1-alcohol, the sealing of jumping a queue was reacted 102 hours down in 30 ℃, filter, the ether detersive enzyme adds an amount of column chromatography silica gel, and decompression is spin-dried for into solid, cross post (sherwood oil: ethyl acetate=10: 1), product (S)-1-ethynyl-2-butyl-2,3-divinyl-1-alcohol 50mg (ee:＞99%, y:41%) and (R)-acetate-1-ethynyl-2-butyl-2,3-divinyl-1-alcohol ester 59mg (ee:97.2%, y:46%).
(S)-and 1-ethynyl-2-butyl-2,3-divinyl-1-alcohol: liquid;
1H NMR (300MHz, CDCl
3) δ 5.00-4.90 (m, 2H), 4.90-4.78 (m, 1H), 2.51 (d, J=2.1Hz, 1H), 2.33 (s, 1H), 2.18-2.00 (m, 2H), 1.50-1.20 (m, 4H), 0.89 (t, J=7.2Hz, 3H);
13C NMR (75.4MHz, CDCl
3) δ 204.37,105.40,82.69,79.83,73.46,62.83,29.55,27.24,22.29,13.85; MS (m/z) 126 (M
+, 0.17); IR (neat) 3307,2117,1959cm
-1HRMS (M
+), C
10H
14O, calculated value: 150.1045, measured value: 150.1088.
(R)-and acetate-1-ethynyl-2-butyl-2,3-divinyl-1-alcohol ester: liquid;
1H NMR (300MHz, CDCl
3) δ 5.85-5.80 (m, 1H), 5.92-4.85 (m, 2H), 2.51 (d, J=1.8Hz, 1H), 2.06 (s, 3H), 1.50-1.22 (m, 4H), 0.88 (t, J=7.2Hz, 3H); MS (m/z) 149 (M
+-COCH
3, 3.77); IR (neat) 2124.4,1959.7,1746.3cm
-1HRMS (M
+-COCH
3), C
10H
13The O calculated value: 149.0967, measured value: 149.0978.
Embodiment 16
(S)-and 1-ethynyl-2-styroyl-2,3-divinyl-1-pure and mild (R)-acetate-1-ethynyl-2-styroyl-2,3-divinyl-1-alcohol ester
Get the round-bottomed flask of a 25ml, add 70mg enzyme such as embodiment 2, the 5ml vinyl acetate, 1-ethynyl-2-styroyl-2 that 100mg disappears outward, 3-divinyl-1-alcohol, the sealing of jumping a queue was reacted 102 hours down in 30 ℃, filter, the ether detersive enzyme adds an amount of column chromatography silica gel, and decompression is spin-dried for into solid, cross post (sherwood oil: ethyl acetate=10: 1), product (S)-1-ethynyl-2-styroyl-2,3-divinyl-1-alcohol 40mg (ee:99.9%, y:40%) and (R)-acetate-1-ethynyl-2-styroyl-2,3-divinyl-1-alcohol ester 53mg (ee:99.8%, y:44%)
(S)-and 1-ethynyl-2-styroyl-2,3-divinyl-1-alcohol: liquid;
1H NMR (300MHz, CDCl
3) δ 7.40-7.18 (m, 5H), 5.08-4.98 (m, 2H), 4.90-4.80 (m, 1H), 2.81 (t, J=8.1Hz, 2H), 2.54 (d, J=2.4Hz, 1H), 2.50-2.40 (m, 2H), 2.20 (s, 1H);
13C NMR (75.4MHz, CDCl
3) δ 204.69,141.61,128.039,128.27,125.89,104.78,82.49,80.34,73.78,62.98,33.78,29.18; MS (m/z) 198 (M
+, 3.72); IR (neat) 3393,2117,1957cm
-1HRMS (M
+), C
14H
14O, calculated value: 198.1045, measured value: 198.1056.
(R)-and acetate-1-ethynyl-2-styroyl-2,3-divinyl-1-alcohol ester: liquid;
1H NMR (300MHz, CDCl
3) δ 7.30-7.10 (m, 5H), 5.90-5.85 (m, 1H), 5.00-4.82 (m, 2H), 2.74 (t, J=7.8Hz, 2H), 2.49 (d, J=2.1Hz, 1H), 2.49-2.24 (m, 2H), 2.03 (s, 3H);
13C NMR (75.4MHz, CDCl
3) δ 206.47,169.39,141.41,128.30,125.86,100.97,79.38,79.09,74.59,64.52,33.61,29.15,20.82; MS (m/z) 197 (M
+-COCH
3, 10.80); IR (neat) 2124.4,1959,1744cm
-1HRMS (M
+-COCH
3), C
14H
13The O calculated value: 197.0967, measured value: 197.0961.
Embodiment 17
(S)-and 1-ethynyl-2-phenmethyl-2,3-divinyl-1-pure and mild (R)-acetate-1-ethynyl-2-phenmethyl-2,3-divinyl-1-alcohol ester
Get the round-bottomed flask of a 25ml, add 70mg enzyme such as embodiment 1, the 5ml vinyl acetate, 1-ethynyl-2-phenmethyl-2 that 100mg disappears outward, 3-divinyl-1-alcohol, the sealing of jumping a queue was reacted 102 hours down in 30 ℃, filter, the ether detersive enzyme adds an amount of column chromatography silica gel, and decompression is spin-dried for into solid, cross post (sherwood oil: ethyl acetate=10: 1), product (S)-1-ethynyl-2-phenmethyl-2,3-divinyl-1-alcohol 42mg (ee:99.5, y:42%) and (R)-acetate-1-ethynyl-2-phenmethyl-2,3-divinyl-1-alcohol ester 53mg (ee:98.2%, y:43%).
(S)-and 1-ethynyl-2-phenmethyl-2,3-divinyl-1-alcohol: liquid; MS (m/z) 184 (M
+, 3.38); IR (neat) 3385,2117,1959cm
-1HRMS (M
+), C
13H
12O, calculated value: 184.0888, measured value: 184.0916.
(R)-and acetate-1-ethynyl-2-phenmethyl-2,3-divinyl-1-alcohol ester: liquid;
1H NMR (300MHz, CDCl
3) δ 7.22-7.12 (m, 5H), 5.80-5.76 (m, 1H), 4.84-4.78 (m, 2H), 3.42-3.36 (m, 2H), 2.49-2.46 (m, 1H), 1.91 (s, 3H);
13C NMR (75.4MHz, CDCl
3) δ 207.35,169.42,138.29,128.94,128.21,126.39,101.10,79.08,78.83,74.76,64.00,35.11,20.70; MS (m/z) 183 (M
+-COCH
3, 26.46); IR (neat) 2124,1960,1744cm
-1HRMS (M
+), C
15H
14O
2Calculated value: 226.0994 measured values: 226.1017
Embodiment 18
(S)-and 1-ethynyl-2-ethoxyl methyl-2,3-divinyl-1-pure and mild (R)-acetate-1-ethynyl-2-ethoxyl methyl-2,3-divinyl-1-alcohol ester
Get the round-bottomed flask of a 25ml, add 70mg enzyme such as embodiment 1, the 5ml vinyl acetate, 1-ethynyl-2-butyl-2 that 100mg disappears outward, 3-divinyl-1-alcohol, the sealing of jumping a queue was reacted 102 hours down in 30 ℃, filter, the ether detersive enzyme adds an amount of column chromatography silica gel, and decompression is spin-dried for into solid, cross post (sherwood oil: ethyl acetate=10: 1), product (S)-1-ethynyl-2-butyl-2,3-divinyl-1-alcohol 44mg (ee:97.8%, y:44%) and (R)-acetate-1-ethynyl-2-butyl-2,3-divinyl-1-alcohol ester 53mg (ee:98.7%, y:42%).
(S)-and 1-ethynyl-2-ethoxyl methyl-2,3-divinyl-1-alcohol: liquid;
1H NMR (300MHz, CDCl
3) δ 5.15-4.84 (m, 3H), 4.34 (d, J=10.8Hz, 1H), 4.09 (d, J=11.1Hz, 1H), 3.52 (q, J=6.9Hz, 2H), 3.45 (s, 1H), 2.54 (s, 1H), 1.19 (t, J=7.2Hz, 3H);
13C NMR (75.4MHz, CDCl
3) δ 205.96,100.73,82.30,78.04,73.56,68.80,65.65,61.94,14.80; MS (m/z) 123 (M
+-C
2H
5, 8.51); HRMS (M
+), C
9H
12O
2, calculated value: 152.0837, measured value: 152.0858.
(R)-and acetate-1-ethynyl-2-ethoxyl methyl-2,3-divinyl-1-alcohol ester: liquid;
1H NMR (300MHz, CDCl
3) δ 6.02-5.94 (m, 1H), 5.08-5.00 (m, 2H), 4.18-4.08 (m, 2H), 3.49 (q, J=6.9Hz, 2H), 2.60-2.55 (m, 1H), 2.10 (s, 3H), 1.20 (t, J=6.9Hz, 3H);
13C NMR (75.4MHz, CDCl
3) δ 207.03,169.47,98.88,78.93,78.70,74.64,65.28,61.92,20.72,14.82; MS (m/z) 149 (M
+-COCH
3, 3.77); IR (neat) 2126,1960,1745cm
-1
Embodiment 19
(S)-and 1-vinyl-2-phenmethyl-2,3-divinyl-1-pure and mild (R)-acetate-1-vinyl-2-phenmethyl-2,3-divinyl-1-alcohol ester
Get the round-bottomed flask of a 25ml, add 70mg enzyme such as embodiment 2, the 5ml vinyl acetate, 1-vinyl-2-phenmethyl-2 that 100mg disappears outward, 3-divinyl-1-alcohol, the sealing of jumping a queue was reacted 102 hours down in 30 ℃, filter, the ether detersive enzyme adds an amount of column chromatography silica gel, and decompression is spin-dried for into solid, cross post (sherwood oil: ethyl acetate=10: 1), product (S)-1-vinyl-2-phenmethyl-2,3-divinyl-1-alcohol 42mg (ee:99.4%, y:42%) and (R)-acetate-1-vinyl-2-phenmethyl-2,3-divinyl-1-alcohol ester 51mg (ee:99.6%, y:42%).
(S)-and 1-vinyl-2-phenmethyl-2,3-divinyl-1-alcohol: liquid;
1H NMR (300MHz, CDCl
3) δ liquid;
1HNMR (300MHz, CDCl
3) δ 7.38-7.20 (m, 5H), 5.96-5.82 (m, 1H), 5.36-5.18 (m, 2H), 4.92-4.88 (m, 2H), 4.50 (s, 1H), 3.48-3.24 (m, 2H), 1.91 (d, J=5.1Hz, 1H);
13C NMR (75.4MHz, CDCl
3) δ 205.23,138.91,138.37,128.92,128.14,126.16,115.79,106.06,78.83,72.05,35.30; MS (m/z) 186 (M
+, 0.99); IR (neat) 3380,1957cm
-1HRMS (M
+), C
13H
14O, calculated value: 186.1045, measured value: 186.0999.
(R)-and acetate-1-vinyl-2-phenmethyl-2,3-divinyl-1-alcohol ester: liquid;
1H NMR (300MHz, CDCl
3) δ 7.24-7.10 (m, 5H), 5.84-5.70 (m, 1H), 5.61-5.56 (m, 1H), 5.24-5.10 (m, 2H), 4.80-4.68 (m, 2H), 3.29-3.20 (m, 2H), 1.89 (s, 3H);
13C NMR (75.4MHz, CDCl
3) δ 207.22,169.83,138.28,128.88,128.10,126.21,117.42,102.35,78.01,73.96,35.62,20.88; MS (m/z) 185 (M
+-COCH
3, 5.99); IR (neat) 2124.4,1959.7,1746.3cm
-1HRMS (M
+-COCH
3), C
10H
13The O calculated value: 185.0967, measured value: 185.0975.
Embodiment 20
(S)-and 3-butyl-2-methyl-4-allyl group-2, the 5-dihydrofuran
Under the nitrogen protection, in reaction tubes, add 140mg (S)-1-methyl-2-butyl-2,3-divinyl-1-alcohol, 1ml acetone, 1ml water, 170mg Silver Nitrate; stirring heating back flow reaction eight hours; add 60ml ether cancellation reaction, saturated sodium chloride aqueous solution washing ether layer three times, water layer is stripped once with the 60ml ether; merge organic layer; anhydrous sodium sulfate drying adds an amount of column chromatography silica gel, and decompression is spin-dried for into solid; cross post (sherwood oil: ethyl acetate=100: 1), get product
(S)-and 3-butyl-2-methyl-2,5-dihydrofuran: liquid;
1H NMR (300MHz, CDCl
3) δ 5.40-5.26 (m, 1H), 4.77-3.97 (m, 3H), 2.09-1.77 (m, 2H), 1.54-1.20 (m, 5H), 1.14 (d, J=5.4Hz 2H), 0.834 (t, J=6.6Hz, 3H);
13C NMR (75.40 MHz, CDCl
3) δ 144.34,118.24,82.94,74.06,29.48,26.47,22.53,20.43,13.91; MS (m/e) 140 (M
+, 8.32); IR (neat) 1661.8 cm
-1, 1083.3 cm
-1, 1018.2 cm
-1HRMS, C
9H
16O: calculated value: 140.1201, measured value: 140.1219.
Embodiment 21
(S)-and 3-butyl-2-methyl-4-allyl group-2, the 5-dihydrofuran
Under the room temperature, with 6ml N,N-dimethylacetamide, 0.605g allyl bromide 98,9mg palladium chloride, 140mg (S)-1-methyl-2-butyl-2,3-divinyl-1-alcohol mixes stirring and added 60ml ether cancellation reaction in 14 hours, saturated sodium chloride aqueous solution washing ether layer three times, water layer is stripped once with the 60ml ether, merges organic layer, anhydrous sodium sulfate drying, add an amount of column chromatography silica gel, decompression is spin-dried for into solid, crosses post (sherwood oil: ethyl acetate=100: 1), get product
(S)-and 3-butyl-2-methyl-4-allyl group-2,5-dihydrofuran: liquid;
1H?NMR(300?MHz，CDCl
3)δ?5.80-5.60(m，1H)，5.11-4.90(m，2H)，4.90-4.71(m，2H)，2.81(d，J＝6.3Hz，2H)，2.26-2.03(m，1H)，2.00-1.83(m，1H)，1.54-1.03(m，7H)，0.89(t，J＝6.3Hz)；
13C?NMR(75.40?MHz，CDCl
3)δ?136.53，135.14，128.97，115.67，83.87，76.13，30.17，29.72，24.51，22.71，20.59，13.85；MS(m/e)180(M
+，3.00)；IR(neat)1638.87?cm
-1，1071.41?cm
-1；
Embodiment 22
(S, S)-2-butyl-3-methyl-2-(1-phenyl-thiazolinyl)-epoxy:
Under the anhydrous and oxygen-free condition, in reaction tubes, add 140mg (S)-1-methyl-2-butyl-2,3-divinyl-1-alcohol, 3ml N, dinethylformamide, 58mg four triphenyl phosphorus palladiums, 3.5 mmole iodobenzenes, 5 mmole salt of wormwood got product in 18 hours in 75-80 ℃ of following stirring reaction
(S, S)-2-butyl-3-methyl-2-(1-phenyl-thiazolinyl)-epoxy: liquid;
1H NMR (300MHz, CDCl
3) δ 7.31-7.19 (m, 5H), 5.37 (dd, J=1.5Hz, J=13.8Hz, 2H), 3.07 (q, J=5.4Hz, 1H), 1.80-1.6 (m, 1H), 1.31-1.02 (m, 8H), 0.80 (t, J=2.6Hz, 3H);
13C NMR (75.40MHz, CDCl
3) δ 148.38,138.49,128.28,127.69,126.46,112.73,64.83,60.84,28.72,27.13,22.58,13.87,13.77; MS (m/e) 216 (M
+, 13.91); IR (neat) 1626.58cm
-115474.78cm
-1, 1493.32cm
-1, 1070.31cm
-1, 1028.11cm
-1HRMS, C
15H
20O: calculated value: 216.15141, measured value: 216.1513.
Claims (8)
1. a class is optically active 2, and 3-connection enol or connection enol ester compound is characterized in that structural formula is:
Wherein, R
2Be C
1～C
10Alkyl and thiazolinyl, C
1～C
10Alkynyl, benzyl, PhCH
2CH
2-or C
1～C
10Alkoxyl group; R
1Be C
1～3Alkyl, vinyl, ethynyl; R
3Be H, C
1-3Alkyl; R
4Be C
1～3Alkyl, phenyl;
Perhaps R
2Be ethoxyl methyl, R
1Be ethynyl, R
3Be H and R
4Be methyl.
2. a class as claimed in claim 1 is optically active 2, and 3-connection enol or connection enol ester compound is characterized in that its structural formula is as follows:
3. the synthetic described class of claim 1 is optically active 2, and the method for 3-connection enol or connection enol ester compound is characterized in that in organic solvent structural formula is
Racemic enol, structural formula be
Acylating reagent under lipase catalysis, obtain optically active 2; the pure and mild enol ester of 3-divinyl-1-; separate; wherein temperature of reaction is 0～80 ℃; reaction times is 3～168 hours; the weight ratio of racemic enol and lipase is 1: 0.05～10, and the mol ratio of racemic enol and acylating reagent is 1: 0.5～50, wherein R
1-R
4According to claim 1, R
5Be hydrogen, C
1～3Alkyl.
4. method as claimed in claim 3 is characterized in that described lipase is the false unicellular lipase of lipase from candida sp, fluorescence, cylinder lipase from candida sp, porcine pancreatic lipase, candida rugosa lipase or false unicellular lipase.
5. method as claimed in claim 3 is characterized in that described organic solvent is normal hexane, hexanaphthene, vinyl acetate, methylene dichloride, acetone, ether or isopropyl ether.
6. method as claimed in claim 3 is characterized in that the reaction times is 10～96 hours.
7. method as claimed in claim 3 is characterized in that temperature of reaction is 25～60 ℃.
8. a class as claimed in claim 1 is optically active 2, and the purposes of 3-connection enolization compound is characterized in that being used to prepare optically active epoxy compounds, amino alcohol or furan derivatives.
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| CN 02112225 CN1386730A (en) | 2002-06-25 | 2002-06-25 | Optically active 2,3-bienol and bienol ester, and synthesizing process and use thereof |
| CNB021543690A CN1304346C (en) | 2002-06-25 | 2002-11-29 | Optically active 2,3-dienol and dienol ester and their synthesis and use |
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