有機(jī)化學(xué)有機(jī)合成路線設(shè)計原理講解課件

2022/12/231IntroductiontoOrganicSynthesis

有機(jī)合成簡介2022/12/171IntroductiontoOrg2022/12/232合成化學(xué)家在舊的自然界旁又建起了一個新的自然界。

——R.B.Woodward2022/12/172合成化學(xué)家在舊的自然界旁又建起了一個新2022/12/233E.J.CoreyRetrosyntheticanalysis

TheNoblePrizein1990

2022/12/173E.J.Corey2022/12/2341.Retrosyntheticanalysis(逆合成分析)

Inthisprocedurethetargetmoleculeistransformedprogressivelyintosimplerstructuresbydisconnectingselectedcarbon-carbonbonds.Thesedisconnectionsrestontransforms,whicharethereverseofplausiblesyntheticconstructions.Eachsimplerstructure,sogenerated,becomesthestartingpointforfurtherdisconnections,leadingtoabranchedsetofinterrelatedintermediates.Aretrosynthetictransformisdepictedbythe=>symbol,asshowninnextslide.Onceacompleteanalysishasbeenconducted,thedesiredsynthesismaybecarriedoutbyapplicationofthereactionsunderlyingthetransforms.

2022/12/1741.Retrosynthetica2022/12/235SynthonEquivalentDisconnectionrestontransforms2022/12/175SynthonEquivalentDi2022/12/2362022/12/1762022/12/237Synthon（合成子)Equivalent（等價物）PolarInversion極性反轉(zhuǎn)2022/12/177Synthon（合成子)Eq2022/12/238PolarInversion極性反轉(zhuǎn)2022/12/178PolarInversion2022/12/239Symbol2022/12/179Symbol2022/12/2310策略1FunctionalGrouptransforms（官能團(tuán)轉(zhuǎn)換）2022/12/1710策略1FunctionalGro2022/12/23112022/12/17112022/12/2312策略2.DisconnectiononTMswithoutFG

（無官能團(tuán)時的切斷策略）——addingFG（添加官能團(tuán)）2022/12/1712策略2.Disconnection2022/12/23132022/12/17132022/12/23142022/12/17142022/12/2315策略3.DisconnectiononTMswithmonoFG3.1ApplicationofMalonicester（丙二酸二酯，活潑亞甲基）2022/12/1715策略3.Disconnection2022/12/23162022/12/17162022/12/23172022/12/17172022/12/231880%99%80%

2022/12/171880%2022/12/2319酮式烯醇式3.2ApplicationofEthylAcetoacetate（乙酰乙酸乙酯）

pKa

＝112022/12/1719酮式2022/12/23202022/12/17202022/12/23212022/12/17212022/12/23222022/12/17222022/12/23233.3ApplicationofEpoxycompounds（環(huán)氧化物）2022/12/17233.3Applicationof2022/12/23242022/12/17242022/12/23252022/12/17252022/12/23263.4DisconnectiononCyclohexene（環(huán)己烯）a)D-A反應(yīng)2022/12/17263.4Disconnection2022/12/23272022/12/17272022/12/2328Birch還原b)Birch還原2022/12/1728Birch還原b)Birch還原2022/12/23294.DisconnectiononBifunctionalgroups

（雙官能團(tuán)化合物）（1）,-unsaturatedcompounds2022/12/17294.Disconnectiono2022/12/23302022/12/17302022/12/2331（2）,-unsaturatedcarboxylicacid2022/12/1731（2）,-unsaturate2022/12/2332（3）-Hydroxyester2022/12/1732（3）-Hydroxyester2022/12/23332022/12/17332022/12/2334（4）1,3-bicarbonyl（1,3-二羰基化合物）

2022/12/1734（4）1,3-bicarbonyl2022/12/23352022/12/17352022/12/2336（5）1,4-bicarbonyl（1,4-二羰基化合物）2022/12/1736（5）1,4-bicarbonyl2022/12/2337（6）1,5-bicarbonyl——邁克爾（Michael）加成反應(yīng)

2022/12/1737（6）1,5-bicarbonyl2022/12/23382022/12/17382022/12/23392022/12/17392022/12/23402022/12/17402022/12/2341（7）1,6-bicarbonyl2022/12/1741（7）1,6-bicarbonyl2022/12/23422022/12/17422022/12/2343Birch還原2022/12/1743Birch還原2022/12/23444.Rearrangment2022/12/17444.Rearrangment2022/12/2345嚬哪醇重排：

2022/12/1745嚬哪醇重排：2022/12/23462022/12/17462022/12/2347習(xí)題嘗試逆合成分析并合成以下目標(biāo)化合物）

2022/12/1747習(xí)題嘗試逆合成分析并合成以下目標(biāo)化2022/12/2348IntroductiontoOrganicSynthesis

有機(jī)合成簡介2022/12/171IntroductiontoOrg2022/12/2349合成化學(xué)家在舊的自然界旁又建起了一個新的自然界。

——R.B.Woodward2022/12/172合成化學(xué)家在舊的自然界旁又建起了一個新2022/12/2350E.J.CoreyRetrosyntheticanalysis

TheNoblePrizein1990

2022/12/173E.J.Corey2022/12/23511.Retrosyntheticanalysis(逆合成分析)

Inthisprocedurethetargetmoleculeistransformedprogressivelyintosimplerstructuresbydisconnectingselectedcarbon-carbonbonds.Thesedisconnectionsrestontransforms,whicharethereverseofplausiblesyntheticconstructions.Eachsimplerstructure,sogenerated,becomesthestartingpointforfurtherdisconnections,leadingtoabranchedsetofinterrelatedintermediates.Aretrosynthetictransformisdepictedbythe=>symbol,asshowninnextslide.Onceacompleteanalysishasbeenconducted,thedesiredsynthesismaybecarriedoutbyapplicationofthereactionsunderlyingthetransforms.

2022/12/1741.Retrosynthetica2022/12/2352SynthonEquivalentDisconnectionrestontransforms2022/12/175SynthonEquivalentDi2022/12/23532022/12/1762022/12/2354Synthon（合成子)Equivalent（等價物）PolarInversion極性反轉(zhuǎn)2022/12/177Synthon（合成子)Eq2022/12/2355PolarInversion極性反轉(zhuǎn)2022/12/178PolarInversion2022/12/2356Symbol2022/12/179Symbol2022/12/2357策略1FunctionalGrouptransforms（官能團(tuán)轉(zhuǎn)換）2022/12/1710策略1FunctionalGro2022/12/23582022/12/17112022/12/2359策略2.DisconnectiononTMswithoutFG

（無官能團(tuán)時的切斷策略）——addingFG（添加官能團(tuán)）2022/12/1712策略2.Disconnection2022/12/23602022/12/17132022/12/23612022/12/17142022/12/2362策略3.DisconnectiononTMswithmonoFG3.1ApplicationofMalonicester（丙二酸二酯，活潑亞甲基）2022/12/1715策略3.Disconnection2022/12/23632022/12/17162022/12/23642022/12/17172022/12/236580%99%80%

2022/12/171880%2022/12/2366酮式烯醇式3.2ApplicationofEthylAcetoacetate（乙酰乙酸乙酯）

pKa

＝112022/12/1719酮式2022/12/23672022/12/17202022/12/23682022/12/17212022/12/23692022/12/17222022/12/23703.3ApplicationofEpoxycompounds（環(huán)氧化物）2022/12/17233.3Applicationof2022/12/23712022/12/17242022/12/23722022/12/17252022/12/23733.4DisconnectiononCyclohexene（環(huán)己烯）a)D-A反應(yīng)2022/12/17263.4Disconnection2022/12/23742022/12/17272022/12/2375Birch還原b)Birch還原2022/12/1728Birch還原b)Birch還原2022/12/23764.DisconnectiononBifunctionalgroups

（雙官能團(tuán)化合物）（1）,-unsaturatedcompounds2022/12/17294.Disconnectiono2022/12/23772022/12/17302022/12/2378（2）,-unsaturatedcarboxylicacid2022/12/1731（2）,-unsaturate2022/12/2379（3）-Hydroxyester2022/12/1732（3）-Hydroxyester2022/12/23802022/12/1