CN106946823B - 一种不对称合成(r)-天然茉莉内酯的方法 - Google Patents

一种不对称合成(r)-天然茉莉内酯的方法 Download PDF

Info

Publication number
CN106946823B
CN106946823B CN201611262264.XA CN201611262264A CN106946823B CN 106946823 B CN106946823 B CN 106946823B CN 201611262264 A CN201611262264 A CN 201611262264A CN 106946823 B CN106946823 B CN 106946823B
Authority
CN
China
Prior art keywords
reaction
natural
jasminolide
hydroxy
synthesizing
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201611262264.XA
Other languages
English (en)
Other versions
CN106946823A (zh
Inventor
张国清
杨大志
袁西福
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Beijing Asrl Technology Co ltd
Original Assignee
Beijing Asrl Technology Co ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Beijing Asrl Technology Co ltd filed Critical Beijing Asrl Technology Co ltd
Priority to CN201611262264.XA priority Critical patent/CN106946823B/zh
Publication of CN106946823A publication Critical patent/CN106946823A/zh
Application granted granted Critical
Publication of CN106946823B publication Critical patent/CN106946823B/zh
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07DHETEROCYCLIC COMPOUNDS
    • C07D309/00Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
    • C07D309/16Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
    • C07D309/28Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
    • C07D309/30Oxygen atoms, e.g. delta-lactones
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07BGENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B53/00Asymmetric syntheses
    • CCHEMISTRY; METALLURGY
    • C07ORGANIC CHEMISTRY
    • C07BGENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07Optical isomers

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

本发明公开了一种不对称合成(R)‑天然茉莉内酯的方法。该方法以(Z)‑3‑己烯‑1‑醇1为起始原料,用DMP试剂氧化为(Z)‑3‑己烯醛2。然后在(R,R)‑ProPhenol配体与二甲基锌存在下,与炔丁酸甲酯发生不对称加成反应,得到(S,Z)‑5‑羟基‑7‑癸烯‑3‑炔酸甲酯3。再在CuI催化下,用NaBH4将三键还原为单键,生成(R,Z)‑5‑羟基‑7‑癸烯酸甲酯4。最后用对甲苯磺酸处理,关环得到目标产物(R)‑天然茉莉内酯。本发明合成路线简捷,反应条件温和,总产率为42%,产物光学纯度为95%。

Description

一种不对称合成(R)-天然茉莉内酯的方法
技术领域
本发明涉及一种新的不对称合成(R)-天然茉莉内酯的方法,属于香料香精化学领域。
背景技术
天然茉莉内酯(Jasmine lactone)存在于茉莉、栀子花、晚香玉等精油中,也存在于桃、杏等水果中(Tressl,R.;Garbe,L.A.;Haffner,T.;Lange,H.ACS Symp.Ser.,1998,705,167-180.),是一种重要的香料(Bourdineaud,J.P.;Ehret,C.;Petrzilka,M.;PatentWO9407887A1,1994,4,14.)。天然茉莉内酯的手性结构对其香气特征具有重要的影响。(R)-天然茉莉内酯,最早发现存在于茉莉精油中(Winter,M.;Malet,G.;Pfeiffer,M.;Demole,E.Helv.Chim.Acta 1962,45,1250-1255.),具有茉莉、坚果、牛奶等香味,香气飘逸(Nohira,H.;Mizuguchi,K.;Murata,T.;Yazaki,Y.;Kanazawa,M.;Aoki,Y.;Nohira,M.Heterocycles 2000,52,1359-1370.)。(S)-天然茉莉内酯,最早发现存在晚香玉中(Kaiser,R.;Lamparsky,D.Tetrahedron Lett.,1976,1659-1660.),具有晚香玉、脂肪、奶油等香味,香气厚重(Nohira,H.;Mizuguchi,K.;Murata,T.;Yazaki,Y.;Kanazawa,M.;Aoki,Y.;Nohira,M.Heterocycles 2000,52,1359-1370.)。(R)-天然茉莉内酯的结构式如式1所示,其结构最重要的是5位的手性碳原子。
Figure BDA0001200011990000011
天然茉莉内酯(Jasmine lactone)可作为茉莉花香型的日用香精的主香剂,广泛用于个人护理产品、化妆品、空气清新剂等,也可用于食品工业(余芳芳;吕星鑫;吕耀宏,化学世界2016,121-128.)。目前日用化学品与食品工业使用的天然茉莉内酯,均为外消旋体,不仅造成原料浪费,也影响化妆品与食品的香味逼真性。因而,研究合成光学纯的天然茉莉内酯,进而考虑替代外消旋的天然茉莉内酯具有重要的应用价值。目前,合成(R)-天然茉莉内酯的方法主要有三种,即手性试剂拆分法、酶催化法与不对称催化法。
(1)手性试剂拆分法是先将外消旋的天然茉莉内酯用NaOH水解为羟基酸,然后与光学纯的手性胺生成两种非对映异构体的混合物,用合适的溶剂进行重结晶,得到非对映体纯的盐,再用NaOH分解盐、酸化得到(R)-羟基酸,最后在对甲苯磺酸的催化下关环得到目标物(R)-天然茉莉内酯(Nohira,H.;Mizuguchi,K.;Murata,T.;Yazaki,Y.;Kanazawa,M.;Aoki,Y.;Nohira,M.Heterocycles 2000,52,1359-1370.)。
(2)酶拆分法是利用Baker酶对外消旋2-羟基己二酸二乙酯进行动力学拆分,得到(S)-2-羟基己二酸二乙酯,再经NaBH4还原、分步保护羟基、环氧化得到环氧羧酸酯,然后经过炔基锂加成、内酯化得到炔基六元环内酯,最后利用Lindar催化氢化生成(R)-天然茉莉内酯Blaser,F.;Deschenaux,P.F.;Kallimopoulos,T.;Jacot-Guillarmod,A.Helv.Chim.Acta,1991,74,787-790.)。
(3)不对称催化法是先利用苏氨酸催化的环戊酮的羟甲基化反应,得到(R)-2-羟甲基环戊酮,然后经m-CPBA氧化得到(R)-羟甲基内酯,再用乙醇钠处理得到二羟基酯,最后经分步保护羟基、环氧化、炔基锂加成、内酯化、Lindar催化氢化等多步反应生成(R)-天然茉莉内酯(Mase,N.;Inoue,A.;Nishio,M.;Takabe,K.Bioorg.Med.Chem.Lett.,2009,19,3955-3958.)。
虽然关于合成(R)-天然茉莉内酯的研究已有几例报道,但现有方法存在需要化学剂量的手性试剂、合成路线繁琐等问题。因此,研究新的、高效的、简捷的合成(R)-天然茉莉内酯的方法,具有重要的意义。
发明内容
本发明旨在提供一种利用醛的不对称炔化反应合成(R)-天然茉莉内酯的新方法。本发明以(Z)-3-己烯-1-醇1为起始原料,用DMP试剂氧化为(Z)-3-己烯醛2。然后在(R,R)-ProPhenol配体与二甲基锌存在下,与丁炔酸甲酯发生不对称加成反应,得到(S,Z)-5-羟基-7-癸烯-3-炔酸甲酯3。再在CuI催化下,用NaBH4将三键还原为单键,生成(R,Z)-5-羟基-7-癸烯酸甲酯4。最后用对甲苯磺酸处理,关环得到目标产物(R)-天然茉莉内酯。本发明合成路线简捷,反应条件温和,总产率为42%,产物光学纯度为95%。本发明合成(R)-天然茉莉内酯的具体路线参见式2。
Figure BDA0001200011990000021
本发明合成(R)-天然茉莉内酯的方法具体包括下列步骤。
(1)(Z)-3-己烯醛2的合成
氩气保护下,(Z)-3-己烯-1-醇1与DMP试剂在二氯甲烷中搅拌反应1h。反应结束后用Na2S2O3与NaHCO3的混合溶液洗涤反应液。分离有机相,水相用二氯甲烷反萃。合并有机相,经干燥、减压浓缩得到粗产物,最后用硅胶柱色谱纯化,制得(Z)-3-己烯醛2。
(2)(S,Z)-5-羟基-7-癸烯-3-炔酸甲酯3的合成
氩气保护下,将(R,R)-ProPhenol配体的甲苯溶液加入丁炔酸甲酯的甲苯溶液中,降温至0℃。加入二甲基锌与(Z)-3-己烯醛2,在0-4℃下搅拌反应24h。反应结束后淬灭反应,分出有机相。水相用乙醚萃取,合并有机相。有机相经干燥、减压浓缩得到粗产物。最后用硅胶柱色谱纯化,制得(S,Z)-5-羟基-7-癸烯-3-炔酸甲酯3。
(3)(R,Z)-5-羟基-7-癸烯酸甲酯4的合成
氩气保护下,将(S,Z)-5-羟基-7-癸烯-3-炔酸甲酯3溶于甲醇。降温至–78℃,加入CuI与NaBH4,搅拌反应30min。反应结束将后,将反应液倒入乙醚与盐酸的混合溶液。分出有机相,水相用乙醚萃取。合并有机相,经干燥、减压浓缩得到粗产物。最后用硅胶柱色谱纯化,制得(R,Z)-5-羟基-7-癸烯酸甲酯4。
(4)(R)-天然茉莉内酯的合成
在(R,Z)-5-羟基-7-癸烯酸甲酯4的二氯甲烷溶液中,0℃下加入对甲苯磺酸。将反应液温度升至室温,继续搅拌反应6h。反应结束后,萃灭反应,分出有机相。水相用二氯甲烷萃取。合并有机相,经干燥、减压浓缩得到粗产物。最后用硅胶柱色谱纯化,制得(R)-天然茉莉内酯。
具体实施方式
实施例1
(Z)-3-己烯醛2的合成
氩气保护下,在50mL Schlenk反应瓶中加入(Z)-3-己烯-1-醇1(2.00g,2mmol)与二氯甲烷20mL,搅拌均匀。将混合液降温至0℃,搅拌下加入DMP试剂(1.02g,2.4mmol)。将反应液缓慢升温至室温,继续搅拌反应1h。反应结束后,将反应液降温至0℃,用Na2S2O3:NaHCO3(1:1)的混合溶液(2×20mL)洗涤。分出有机相,水相用二氯甲烷(2×20mL)萃取,合并有机相,用无水硫酸钠干燥。减压浓缩得到粗产物,用硅胶柱色谱(石油醚/乙酸乙酯15:1)纯化,制得无色油状物(Z)-3-己烯醛2(1.67g,产率85%)。1H NMR(400MHz,CDCl3)δ9.56(t,J=1.9Hz,1H),5.60(dtt,J=10.6,7.2,1.6Hz,1H),5.40(dtt,J=10.6,7.2,1.6Hz,1H),3.07(ddd,J=7.2,1.9,1.5Hz,2H),2.00-1.90(m,2H),0.88(t,J=7.3Hz,3H).HRMS(APCI-TOF)calcd for C6H11O[M+H]+99.0810,found 99.0804.
实施例2
(S,Z)-5-羟基-7-癸烯-3-炔酸甲酯3的合成
氩气保护下,在50mL Schlenk反应瓶中加入丁炔酸甲酯(2.36g,24mmol)与12mL甲苯,加入(R,R)-ProPhenol配体(3.07g,4.8mmol)的甲苯溶液10mL,搅拌均匀。将混合液降温至0℃,用注射器缓慢注入二甲基锌(20mL,1.2M甲苯溶液,24mmol),搅拌2h。在此温度下,缓慢加入(Z)-3-己烯醛2(0.80g,8mmol)。将反应混合液在0-4℃下继续搅拌反应24h。反应结束后,用20mL饱和氯化铵水溶液萃灭反应。分出有机相,水相用乙醚(3×30mL)萃取,合并有机相。用无水Na2SO4干燥,减压浓缩得到粗产物。最后用硅胶柱色谱(石油醚/乙酸乙酯10:1)纯化,制得油状液体(S,Z)-5-羟基-7-烯-3-炔癸酸甲酯3(1.26g,产率80%,光学纯度95%)。[α]D 20=+3.2(c 1.1,CHCl3).1H NMR(400MHz,CDCl3)δ5.96(dtt,J=10.6,7.2,1.6Hz,1H),5.13(dtt,J=10.6,7.2,1.6Hz,1H),3.80(s,3H),2.94(s,2H),2.26(d,J=5.2Hz,1H),2.20-2.16(m,2H),2.02-1.98(m,2H),0.87(t,J=6.8Hz,3H).HRMS(APCI-TOF)calcd forC11H17O3[M+H]+197.1178,found 197.1171.
实施例3
(R,Z)-5-羟基-7-癸烯酸甲酯4的合成
氩气保护下,在100mL Schlenk反应瓶中加入(S,Z)-5-羟基-7-癸烯-3-炔酸甲酯3(1.00g,5mmol)与50mL甲醇,搅拌溶解。将此溶液降温至–78℃,加入CuI(1.91g,10mmol)。在此温度下,缓慢分批加入NaBH4(0.96g,25mmol)。将反应混合液在–78℃下继续搅拌反应30min。反应结束后,剧烈搅拌下,将反应混合物加入200mL乙醚:0.5M盐酸(1:1)的混合溶液中。分出有机相,水相用乙醚(3×100mL)萃取。合并有机相,用无水Na2SO4干燥,减压浓缩得到粗产物。最后用硅胶柱色谱纯化(石油醚/乙酸乙酯15:1),得到无色油状物(R,Z)-5-羟基-7-癸烯酸甲酯4(0.82g,产率82%,光学纯度95%)。[α]D 20=+10.2(c 1.0,EtOH).1H NMR(400MHz,CDCl3)δ5.90(dtt,J=10.5,7.2,1.5Hz,1H),5.11(dtt,J=10.5,7.2,1.5Hz,1H),3.81(s,3H),3.30-3.23(m,1H),2.24(d,J=5.1Hz,1H),2.20-2.11(m,4H),2.01-1.96(m,2H),1.56-1.45(m,4H),0.88(t,J=6.7Hz,3H).HRMS(APCI-TOF)calcd for C11H21O3[M+H]+201.1491,found 201.1485.
实施例4
(R)-天然茉莉内酯的合成
在50mL反应瓶中加入(R,Z)-5-羟基-7-癸烯酸甲酯4(0.80g,4mmol)和30mL二氯甲烷,室温下搅拌溶解。将此溶液降温至0℃,加入对甲苯磺酸(0.069g,0.4mmol)。将反应混合液自然升温至室温,继续搅拌反应6h。反应结束后,加入5mL水萃灭反应。分出有机相,水相用二氯甲烷(3×10mL)萃取。合并有机相,用饱和食盐水50mL洗涤,经无水Na2SO4干燥,减压浓缩得到粗产物。最后用硅胶柱色谱(石油醚/乙酸乙酯20:1)纯化,得到无色油状物(R)-天然茉莉内酯(0.52g,产率76%,光学纯度95%)。[α]D 20=-16.6(c 0.9,CHCl3).1HNMR(400MHz,CDCl3)δ5.40(dtt,J=10.6,7.1,1.6Hz,1H),5.22(dtt,J=10.6,7.1,1.6Hz,1H),4.35-4.26(m,1H),2.58-2.30(m,4H),2.08-2.00(m,2H),1.98-1.55(m,4H),0.99(t,J=6.8Hz,3H).HRMS(APCI-TOF)calcd for C10H17O2[M+H]+169.1229,found 169.1220。

Claims (5)

1.一种不对称合成(R)-天然茉莉内酯的方法,其特征在于包括如下步骤:先用DMP试剂将(Z)-3-己烯-1-醇氧化为(Z)-3-己烯醛,然后在(R,R)-ProPhenol配体与二甲基锌存在下,与丁炔酸甲酯发生不对称加成反应,合成(S,Z)-5-羟基-7-癸烯-3-炔酸甲酯;再在CuI催化下,用NaBH4还原为(R,Z)-5-羟基-7-癸烯酸甲酯,最后用对甲苯磺酸处理,得到目标产物(R)-天然茉莉内酯。
2.根据权利要求1所述的一种不对称合成(R)-天然茉莉内酯的方法,其特征在于合成(Z)-3-己烯醛的方法为:氩气保护下,(Z)-3-己烯-1-醇与DMP试剂在二氯甲烷中搅拌反应,反应结束后用Na2S2O3与NaHCO3的混合溶液洗涤反应液;经分液、萃取、干燥、减压浓缩得到粗产物,最后用硅胶柱色谱纯化,制得(Z)-3-己烯醛。
3.根据权利要求1所述的一种不对称合成(R)-天然茉莉内酯的方法,其特征在于合成(S,Z)-5-羟基-7-癸烯-3-炔酸甲酯的方法为:氩气保护下,将二甲基锌与(Z)-3-己烯醛依次加入(R,R)-ProPhenol配体与丁炔酸甲酯的甲苯溶液,0-4℃下搅拌反应,反应结束后淬灭反应;经分液、萃取、干燥、减压浓缩得到粗产物,最后用硅胶柱色谱纯化,制得(S,Z)-5-羟基-7-癸烯-3-炔酸甲酯。
4.根据权利要求1所述的一种不对称合成(R)-天然茉莉内酯的方法,其特征在于合成(R,Z)-5-羟基-7-癸烯酸甲酯的方法为:氩气保护下,–78℃下,将CuI与NaBH4依次加入(S,Z)-5-羟基-7-癸烯-3-炔酸甲酯的甲醇溶液,搅拌反应,反应结束后,将反应液倒入乙醚与盐酸的混合溶液;经分液、萃取、干燥、减压浓缩得到粗产物,最后用硅胶柱色谱纯化,制得(R,Z)-5-羟基-7-癸烯酸甲酯。
5.根据权利要求1所述的一种不对称合成(R)-天然茉莉内酯的方法,其特征在于合成(R)-天然茉莉内酯的方法为:在0℃下,将对甲苯磺酸加入(R,Z)-5-羟基-7-癸烯酸甲酯的二氯甲烷溶液,升至室温后搅拌反应,反应结束后,萃灭反应;经分液、萃取、干燥、减压浓缩得到粗产物,最后用硅胶柱色谱纯化,制得(R)-天然茉莉内酯。
CN201611262264.XA 2016-12-30 2016-12-30 一种不对称合成(r)-天然茉莉内酯的方法 Active CN106946823B (zh)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201611262264.XA CN106946823B (zh) 2016-12-30 2016-12-30 一种不对称合成(r)-天然茉莉内酯的方法

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
CN201611262264.XA CN106946823B (zh) 2016-12-30 2016-12-30 一种不对称合成(r)-天然茉莉内酯的方法

Publications (2)

Publication Number Publication Date
CN106946823A CN106946823A (zh) 2017-07-14
CN106946823B true CN106946823B (zh) 2022-07-15

Family

ID=59465856

Family Applications (1)

Application Number Title Priority Date Filing Date
CN201611262264.XA Active CN106946823B (zh) 2016-12-30 2016-12-30 一种不对称合成(r)-天然茉莉内酯的方法

Country Status (1)

Country Link
CN (1) CN106946823B (zh)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN110128303B (zh) * 2019-07-04 2020-12-18 中国农业大学 一种合成麝香提取物(2R,5R)-Musclide-A1的方法
CN112898147B (zh) * 2021-02-09 2022-02-11 中国农业大学 一种不对称合成(13r,14s)-13-羟基-14-甲基十六烷酸的方法
CN114831175A (zh) * 2022-05-17 2022-08-02 华中农业大学 一种柑橘保鲜用添加剂及应用

Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07242589A (ja) * 1994-03-08 1995-09-19 Nippon Zeon Co Ltd 光学活性な(z)−5−ヒドロキシ−7−デセン酸の製造法及び光学活性なジャスミンラクトンの製造法

Patent Citations (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPH07242589A (ja) * 1994-03-08 1995-09-19 Nippon Zeon Co Ltd 光学活性な(z)−5−ヒドロキシ−7−デセン酸の製造法及び光学活性なジャスミンラクトンの製造法

Non-Patent Citations (4)

* Cited by examiner, † Cited by third party
Title
"Development of Zn–ProPhenol-Catalyzed Asymmetric Alkyne Addition: Synthesis of Chiral Propargylic Alcohols";Barry M. Trost等;《Chem. Eur. J.》;20121023;第18卷;第16498-16509页 *
"New Synthesis of Jasmine Lactone and Related -Lactones from 1,2-Cyclohexanedione. Preparation and Dye-Sensitized Photooxygenation of 3-(2-Alkenyl)- and 3-(2-Alkynyl)-l,2-cyclohexanediones";Masanori Utaka等;《J. Org. Chem.》;19861231;第51卷(第6期);第935-938页 *
"Synthesis of (-)-(6R)- and (+)-(6S)-tetrahydro-6-[(Z)-pent-2-enyl]-2H-pyran-2-one, lactones from Jasminum grandiflorum L. and from Polianthes tuberosa L";Florian Blaser等;《Helvetica Chimica Acta》;19911231;第74卷(第4期);第787-790页 *
"The first asymmetric total synthesis of (R)-tuberolactone, (S)-jasmine lactone and (R)-d-decalactone";Gowravaram Sabitha等;《Tetrahedron Letters》;20060928;第47卷;第8179-8181页 *

Also Published As

Publication number Publication date
CN106946823A (zh) 2017-07-14

Similar Documents

Publication Publication Date Title
Suggs et al. Synthesis of a chiral rhodium alkyl via metal insertion into an unstrained CC bond and use of the rate of racemization at carbon to obtain rhodium-carbon bond dissociation energy
Deng et al. A practical, highly enantioselective synthesis of the taxol side chain via asymmetric catalysis.
Shigehisa et al. Formal total synthesis of (+)-wortmannin using catalytic asymmetric intramolecular aldol condensation reaction
CN106946823B (zh) 一种不对称合成(r)-天然茉莉内酯的方法
Petersen et al. Palladium-catalyzed, asymmetric Baeyer–Villiger oxidation of prochiral cyclobutanones with PHOX ligands
Cannillo et al. Fast synthesis of complex enantiopure heterocyclic scaffolds by a tandem sequence of simple transformations on α-hydroxyaldehydes.
Vijender et al. Amberlist-15 as heterogeneous reusable catalyst for regioselective ring opening of epoxides with amines under mild conditions
Das et al. Stereoselective total synthesis of (+)-strictifolione and (6R)-6 [(E, 4R, 6R)-4, 6-dihydro-10-phenyl-1-decenyl)-5, 6-dihydro-2H-2-pyrone
Ferrarini et al. Tellurium in organic synthesis: a general approach to buteno-and butanolides
Song et al. Dinuclear zinc catalyzed asymmetric tandem Michael addition/acetalization reactions of cyclic diketones and β, γ-unsaturated α-ketoesters
Nozaki et al. Synthesis of α-Methylene-γ-butyrolactones via Addition of Tin Hydride to Enynes Induced by Triethylborane
CN113861137B (zh) 酮与alpha氯代酮一步反应合成呋喃类化合物的方法
Satoh et al. A novel method for the asymmetric synthesis of 4, 4-disubstituted 2-cyclopentenones from optically active 1-chlorovinyl p-tolyl sulfoxides and its application to the asymmetric total synthesis of (+)-α-cuparenone
JP6054108B2 (ja) 光学活性2,3−ジヒドロファルネサールの製造方法
CN114702475A (zh) 一种单一构型烟碱的合成工艺
Stepanenko et al. Chiral spiroaminoborate ester as a highly enantioselective and efficient catalyst for the borane reduction of furyl, thiophene, chroman, and thiochroman-containing ketones
Halperin et al. Lithium aldol reactions of α-chloroaldehydes provide versatile building blocks for natural product synthesis
He et al. Sharpless AD strategy towards the γ-methyl butenolide unit of acetogenins: Enantioselective synthesis of butenolide I and II with mosquito larvicidal activity
CN106946705B (zh) 一种合成(1r,2s)-二氢茉莉酮酸甲酯的方法
JPH03115246A (ja) ムスコンの製法及び不飽和大環状ケトンの製法
Lattanzi et al. Synthesis of a renewable hydroperoxide from (+)-norcamphor: influence of steric modifications of the bicyclic framework on asymmetric sulfoxidation
CN106588854A (zh) 一种海洋天然产物Puupehenol的合成方法
Yamano et al. Total synthesis of lycopene-5, 6-diol and γ-carotene-5′, 6′-diol stereoisomers and their HPLC separation
CN105646431B (zh) 一种海洋天然产物Puupehenone的合成方法
WO2004043942A1 (ja) γ-ジャスモラクトンの製造方法

Legal Events

Date Code Title Description
PB01 Publication
PB01 Publication
SE01 Entry into force of request for substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant