Physical Organic Chemistry
Physical Organic Chemistry CHEM 6311
University of Memphis
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This 7 page Class Notes was uploaded by Ms. Noemie Klein on Friday October 23, 2015. The Class Notes belongs to CHEM 6311 at University of Memphis taught by Theodore Burkey in Fall. Since its upload, it has received 41 views. For similar materials see /class/228405/chem-6311-university-of-memphis in Chemistry at University of Memphis.
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Date Created: 10/23/15
Chem 6311 Synthesis Warren CH711 page 1 1 Strategy lll Reversal of Polarity 11 occarbonyl position is nucleophilic as enolate or enol 111 reaction with halogen turns position into an electron sink at the a position 92C or OH 1 o EVK 112 halogenation of ketones note the selectivity Br2 O O KPh gt HPh HOAc Br 113 Analyze the following to six carbon starting material WBr Br 114 Halogenation of acids HVZ Br 0 o 2 o HOEt R R gt R jkOH P03 rKBr 03 CI 0 o 2 O HOEt R R gt R lOH OPCI3 ICIKCI IKOEt 115 acid chloride reacts more rapidly than occhloro 116 analysis 1 i 0 Nfcl 2 O NH gt D 02 ON ON 12 ring formations 356 members easy 121 analyze morpholine derivative RN 0 Chem 6311 l A A Synthesis Warren CH711 OH OH gt OH para x B 011 2 mm 20 gt0 13 try analysis ofdiol skip for now page 2 122 analysis of bicyclic ether 7 HO OH HO 2 NtBu I H Retrosynthetic Analysis strategy summary 21 identify functional groups 22 disconnect functional groups interconvert as needed 221 at aromatic rings 222 at CX 2221 two bonds at 11 12 and 13 2222 at ring Synthesis summary 31 add reagents and conditions to analysis 32 check regiochemistry determines order 33 check for unwanted reactions 34 modify plan with protecting groups and conditions 35 Analysis skip 351 recognize functional groups in target molecule 352 disconnect by methods corresponding to reliable reactions OOMNH2 2 O oNCsN Z O OH C N Amine Synthesis 41 direct alkylation usually not useful unless the product is less reactive charge Chem 6311 Synthesis Warren CH711 page 3 i6 i9 RNH2 e ICH2CH3 RNH2 RNH2 ICHZCH3 gt RNHZCHZCH3 RNHCHZCH3 RNH3 gt RNHCH20H32 gt 42 use reagents that give less reactive products and convert to amines 421 acid chlorides ketones aldehydes RNH2 Ol 0 mm g2 gt R CI R NHR R39 NHR NHR RNHz 21 NR NaBH4 CIH R RH R RH Rl Rquot 422 analysis x N o 39H 5 NJ 2M WK 423 advantage of following analysis 0 N2 gt OK NH2 43 Primary amines 431 one step from ammonia imine without substituent unstable NH2 0 NaBH NH 4 NH3 R39ARquot orH2Pt R39ARquot R39IRquot 432 from nitriles after reduction H2Pt02H RBrKCN gt RCN KBr gt RCHzNHz orLiAlH4 1 HClNaN02 H2PdH ArNH2 gt ArCN gt ArCHzNHz 2 CuCN LiAIH4 ArCH2C KCN gt ArCHZCNgt ArCHZCHzNHz AlCl3Et20 433 from phthalimide after acyl transfer only one electron pair ofanion can delocalize Chem 6311 Synthesis Warren CH711 page 4 O O 6 e H2NNH2 NH N K RBr gt NR gt RNH2 NH 0 0 434 branched primary amines avoid elimination by basic cyanide 4341 hydroxylamine reduction ammonia not good due to polymerization 0 e e NaOAc NOH LiAlH4 NH2 HONH Cl gt RIARH 3 RIARquot or HzPt RIARquot 4342 Hoffmann rearrangement or azide 0 Br OH R 2 R 1NH2 gt 1gtrNH2 R2 R2 R3 R3 H2Pt02H RBrKN3 gt RN3 KBr gt RNH2 or LiAlH4 44 analysis Fen uramine NHEt Z F3C 5 Protecting Groups see Warren Table 91 page 68 51 Improves chemoselectivity reduce only the ester OH CE 0 NaBH4 W 0 Mom O MOH o H H LIAIH H20 0 O 4 O O HO OH OEt gt MOH o 52 ketal can protect diols as well as carbonyl compound HO Br 0 Br 0 HQ gt y HO o 0 H0 53 protect aldehyde as acetal Chem 6311 Synthesis Warren CH711 page 5 54 protect ketone as ketal 55 carboxylic acid as ester or anion 551 deprotection of acid or alcohols H O H ngH OH H20 gtHoau 5 5 2 RAO BU 39 R kO Bu RRO 0 H2 0 RAGPh gt RAOH H30ph 553 PdC i i z 2quot g i Zn2 CI Cl Zn 9 R o gt R We 39 R 0 CI Cl 554 CI CI CI 56 alcohol as ether acetal ester ROH j H 0 0 R0 0 THP 561 OMe OMe ROH ClO ROO 562 MEM OMe OMe OMe 1 NaH NalO4OsO4 OH OMEM OMEM 2CIO0Me O H OMe OMe CF CO H OMe NaBH4 NaH 3 2 OH OMEM OCH2 PhCHzBr PhCHZO HO PhCH 0 o 2 MOCH H 563 H 3 57 amine as amide urethane phthalimide 571 disconnect Aspartame from aspartic acid and phenylalanine 572 protect aspartic acid amine 573 Analysis HOZC HOZC H N co Me H 2 2 H2N co H N 002Me 2 OH T Z 2 H2N T H2N Ph Ph 0 Ph 0 574 synthesis protect other acid Chem 6311 Synthesis Warren CH711 page 6 H020 HozC o 0 K OH gt 2L OH N PhO CI HZN Ph 0 H 575 0 0 H020 cr HOZC CI Cl 0 Ho 0 2L OH 2L 0 39 N N PhO H 0 CI CI Ph 0 H or 0 H020 cl cl HOZC 2L 0 T L N COZH N PhO H CI Ph PhO H T o 0 576 Ph 58 thiols as thioester O One group CC disconnections 61 common carboncarbon forming reactions yield alcohol 62 alcohols can be formed from halides and carbonyl compounds BFOA 621 analysis NMe2 NMe2 NMe2 Q 2 g 2 HNM62 0 Ph OJK Ph OH O 0 622 synthesis acid catalyzed esteri cation no good in last step Why NMe2 NMe2 CH3CHZCOCI gt N 0 Ph OH I Ph OJK 623 two identical R groups start with ester and Grignard PhVMgBr l PhA O OH OEt Ph 2MeMgBr O Chem 6311 Synthesis Warren CH711 page 7 624 Analysis QWOH Ph Ph 63 Ketone and aldehydes from alcohol oxidation OH Br 0 06H CGH 2 gtc6H13 H 631 Na20r207 H converts secondary alcohol to ketone primary to carboxylic acid 0 632 Cr03pyridine oxidation of primary alcohol stops at aldehyde 64 Carboxylic acids CC disconnection H 641 RMgBr or Li 002 gt RCOZMgBr gt RCOZH H RBr KCN gt RCN gt RCOZH H20 642 0 O n39C4H9kC 39C4H9kOH O o 0HKOJK 2 o n39 4 9 n39CeH13 643 Q3JlnceH13 Z NC 39CGH13 gtBrn39CeH13 65 12 disconnection alcohol Ph PhMgBr lgtgt 651 Ho 0 66 12 disconnection ketone Ph Ph 61 O OH 6
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