Appendix A. Common Abbreviations, Arrows, and Symbols. Abbreviations

Transcription

1 smi97462_apps.qxd 12/6/04 1:09 PM Page A-1 Appendix A ommon Abbreviations, Arrows, and Symbols Abbreviations Ac acetyl, 3 BBN 9-borabicyclo[3.3.1]nonane BINAP 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl B tert-butoxycarbonyl, ( 3 ) 3 bp boiling point Bu butyl, BS reagent orey Bakshi Shibata reagent DBN 1,5-diazabicyclo[4.3.0]non-5-ene DBU 1,8-diazabicyclo[5.4.0]undec-7-ene D dicyclohexylcarbodiimide DET diethyl tartrate DIBAL- diisobutylaluminum hydride, [( 3 ) 2 2 ] 2 Al DMF dimethylformamide, N( 3 ) 2 DMS dimethyl sulfoxide, ( 3 ) 2 S ee enantiomeric excess Et ethyl, 3 2 FGI functional group interconversion MPA hexamethylphosphoramide, [( 3 ) 2 N] 3 P M highest occupied molecular orbital I infrared LA lithium aluminum hydride, LiAl 4 LDA lithium diisopropylamide, LiN[( 3 ) 2 ] 2 LUM lowest unoccupied molecular orbital m- meta mpba m-chloroperoxybenzoic acid Me methyl, 3 M molecular orbital mp melting point MS mass spectrometry MW molecular weight NBS N-bromosuccinimide NM N-methylmorpholine N-oxide NM nuclear magnetic resonance o- ortho p- para P pyridinium chlorochromate Ph phenyl, 6 5 ppm parts per million Pr propyl, TBDMS tert-butyldimethylsilyl TF tetrahydrofuran TMS tetramethylsilane, ( 3 ) 4 Si UV ultraviolet A-1

2 smi97462_apps.qxd 12/6/04 1:09 PM Page A-2 A-2 APPENDIX A ommon Abbreviations, Arrows, and Symbols Arrows Symbols reaction arrow equilibrium arrows double-headed arrow, used between resonance structures full-headed curved arrow, showing the movement of an electron pair half-headed curved arrow (fishhook), showing the movement of an electron retrosynthetic arrow no reaction dipole hn light heat δ + partial positive charge δ partial negative charge l wavelength n frequency n ~ wavenumber A Brønsted Lowry acid B: Brønsted Lowry base :Nu nucleophile E + electrophile X halogen bond oriented forward bond oriented behind partial bond [ ] transition state [] oxidation [] reduction

3 smi97462_apps.qxd 12/6/04 1:09 PM Page A-3 Appendix B pk a Values for Selected ompounds ompound pk a ompound pk a I 10 Br S S l 7 [( 3 ) 2 ] [ 3 2 ] S N2 0.0 F l ( 3 ) N 3 + N + N N + N N l P F l Br I N F N S S Br N l N Br 4.0 N A-3

4 smi97462_apps.qxd 12/6/04 1:09 PM Page A-4 A-4 APPENDIX B pk a Values for Selected ompounds ompound pk a ompound pk a 3 N 2 Et 3 N N S 10.5 [( 3 ) 3 N] Et 10.7 [ 3 N 3 ] [( 3 ) 2 N 2 ] F N 3 Et N ( 3 ) 3 18 ( 3 ) N 25 l N( 3 ) N N

5 smi97462_apps.qxd 12/6/04 1:09 PM Page A-5 Appendix Bond Dissociation Energies for Some ommon Bonds [A B A + B] Bond o kcal/mol (kj/mol) Z bonds F 136 (569) l 103 (431) Br 88 (368) I 71 (297) 119 (498) Z Z bonds 104 (435) F F 38 (159) l l 58 (242) Br Br 46 (192) I I 36 (151) 51 (213) bonds (435) (410) (410) ( 3 ) 2 95 (397) ( 3 ) 3 91 (381) (435) 125 (523) (364) (460) (356) bonds (368) (356) (385) (489) A-5

6 smi97462_apps.qxd 12/6/04 1:09 PM Page A-6 A-6 APPENDIX Bond Dissociation Energies for Some ommon Bonds [A B A + B] Bond o kcal/mol (kj/mol) X bonds 3 F 109 (456) 3 l 84 (351) 3 Br 70 (293) 3 I 56 (234) 3 2 F 107 (448) 3 2 l 81 (339) 3 2 Br 68 (285) 3 2 I 53 (222) ( 3 ) 2 F 106 (444) ( 3 ) 2 l 80 (335) ( 3 ) 2 Br 68 (285) ( 3 ) 2 I 53 (222) ( 3 ) 3 F 106 (444) ( 3 ) 3 l 79 (331) ( 3 ) 3 Br 65 (272) ( 3 ) 3 I 50 (209) bonds 3 91 (381) (381) (381) ( 3 ) 2 91 (381) ( 3 ) 3 91 (381)

7 smi97462_apps.qxd 12/6/04 1:09 PM Page A-7 Appendix D haracteristic I Absorption Frequencies Bond Functional group Wavenumber (cm 1 ) omment N broad, strong very broad, strong N two peaks 2 N one peak N 2, N one or two peaks; N bending also observed at 1640 cm 1 sp 3300 sharp, often strong sp medium sp strong sp 2 of one or two peaks 2250 medium N 2250 medium strong l 1800 () , 1760 two peaks increasing n ~ with decreasing ring size increasing n ~ with decreasing ring size 2, conjugated N 2, N, increasing n ~ with decreasing N 2 ring size Alkene 1650 medium Arene 1600, 1500 medium N 1650 medium A-7

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9 smi97462_apps.qxd 12/6/04 1:09 PM Page A-9 Appendix E haracteristic 1 NM Absorptions ompound type hemical shift (ppm) Alcohol Aldehyde 9 10 Alkane ~ ~1.3 3 ~1.7 Alkene sp allylic sp Alkyl halide F l Br I A-9

10 smi97462_apps.qxd 12/6/04 1:09 PM Page A-10 A-10 APPENDIX E haracteristic 1 NM Absorptions ompound type hemical shift (ppm) Alkyne ~2.5 Amide N Amine N N Aromatic compound sp benzylic sp arbonyl compound sp 3 on the α carbon arboxylic acid Ether

11 smi97462_apps.qxd 12/15/04 10:10 AM Page A-11 Appendix F General Types of rganic eactions Substitution eactions [1] Nucleophilic substitution at an sp 3 hybridized carbon atom [a] Alkyl halides (hapter 7) X + Nu Nu + X nucleophile [b] Alcohols (Section 9.11) + X X + 2 [c] Ethers (Section 9.14) ' + X X + ' X + 2 X = Br or I [d] Epoxides (Section 9.15) [1] Nu [2] 2 or Z Nu or Z = nucleophile Nu (Z) [2] Nucleophilic acyl substitution at an sp 2 hybridized carbon atom arboxylic acids and their derivatives (hapter 22) Z + Nu nucleophile Nu + Z Z =, l,, ', N' 2 [3] adical substitution at an sp 3 hybridized bond Alkanes (Section 13.3) + X 2 hν or X + X [4] Electrophilic aromatic substitution Aromatic compounds (hapter 18) + E + E + + electrophile A-11

12 smi97462_apps.qxd 12/6/04 1:09 PM Page A-12 A-12 APPENDIX F General Types of rganic eactions Elimination eactions a Elimination at an sp 3 hybridized carbon atom [a] Alkyl halides (hapter 8) X + B base + B + + X new π bond [b] Alcohols (Section 9.8) A + 2 new π bond Addition eactions [1] Electrophilic addition to carbon carbon multiple bonds [a] Alkenes (hapter 10) [b] Alkynes (Section 11.6) + X Y X Y X Y + X Y X Y [2] Nucleophilic addition to carbon oxygen multiple bonds Aldehydes and ketones (hapter 21) + Nu (') nucleophile 2 (') Nu

13 smi97462_apps.qxd 12/6/04 1:09 PM Page A-13 Appendix G ow to Synthesize Particular Functional Groups Acetals eaction of an aldehyde or ketone with two equivalents of an alcohol (21.14) Acid chlorides eaction of a carboxylic acid with thionyl chloride (22.10) Alcohols Nucleophilic substitution of an alkyl halide with or 2 (9.6) ydration of an alkene (10.12) ydroboration oxidation of an alkene (10.16) eduction of an epoxide with LiAl 4 (12.6) eduction of an aldehyde or ketone (20.4) ydrogenation of an α,β-unsaturated carbonyl compound with 2 + Pd- (20.4) Enantioselective reduction of an aldehyde or ketone with the chiral BS reagent (20.6) eduction of an acid chloride with LiAl 4 (20.7) eduction of an ester with LiAl 4 (20.7) eduction of a carboxylic acid with LiAl 4 (20.7) eaction of an aldehyde or ketone with a Grignard or organolithium reagent (20.10) eaction of an acid chloride with a Grignard or organolithium reagent (20.13) eaction of an ester with a Grignard or organolithium reagent (20.13) eaction of an organometallic reagent with an epoxide (20.14B) Aldehydes ydroboration oxidation of a terminal alkyne (11.10) xidation of a 1 alcohol with P (12.12) xidative cleavage of an alkene with 3 followed by Zn or ( 3 ) 2 S (12.10) eduction of an acid chloride with LiAl[( 3 ) 3 ] 3 (20.7) eduction of an ester with DIBAL- (20.7) ydrolysis of an acetal (21.14B) ydrolysis of an imine or enamine (21.12) eduction of a nitrile (22.18B) Alkanes atalytic hydrogenation of an alkene with 2 + Pd- (12.3) atalytic hydrogenation of an alkyne with two equivalents of 2 + Pd- (12.5A) eduction of an alkyl halide with LiAl 4 (12.6) eduction of a ketone to a methylene group ( 2 ) the Wolff Kishner or lemmensen reaction (18.14B) Protonation of an organometallic reagent with 2,, or acid (20.9) A-13

14 smi97462_apps.qxd 12/6/04 1:09 PM Page A-14 A-14 APPENDIX G ow to Synthesize Particular Functional Groups Alkenes Dehydrohalogenation of an alkyl halide with base (8.3) Dehydration of an alcohol with acid (9.8) Dehydration of an alcohol using Pl 3 and pyridine (9.10) β Elimination of an alkyl tosylate with base (9.13) atalytic hydrogenation of an alkyne with 2 + Lindlar catalyst to form a cis alkene (12.5B) Dissolving metal reduction of an alkyne with Na, N 3 to form a trans alkene (12.5) Wittig reaction (21.10) ofmann elimination of an amine (25.12) Alkyl halides eaction of an alcohol with X (9.11) eaction of an alcohol with Sl 2 or PBr 3 (9.12) leavage of an ether with Br or I (9.14) ydrohalogenation of an alkene with X (10.9) alogenation of an alkene with X 2 (10.13) ydrohalogenation of an alkyne with two equivalents of X (11.7) alogenation of an alkyne with two equivalents of X 2 (11.8) adical halogenation of an alkane (13.3) adical halogenation at an allylic carbon (13.10) adical addition of Br to an alkene (13.13) Electrophilic addition of X to a 1,3-diene (16.10) adical halogenation of an alkyl benzene (18.13) alogenation α to a carbonyl group (23.7) Alkynes Dehydrohalogenation of an alkyl dihalide with base (11.5) S N 2 reaction of an alkyl halide with an acetylide anion, (11.11) Amides eaction of an acid chloride with N 3 or an amine (22.8) eaction of an anhydride with N 3 or an amine (22.9) eaction of a carboxylic acid with N 3 or an amine and D (22.10) eaction of an ester with N 3 or an amine (22.11) Amines eduction of a nitro group (18.14) eduction of an amide with LiAl 4 (20.7B) eduction of a nitrile (22.18B) S N 2 reaction using N 3 or an amine (25.7A) Gabriel synthesis (25.7A) eductive amination of an aldehyde or ketone (25.7) Amino acids S N 2 reaction of an α-halo carboxylic acid with excess N 3 (28.2A) Alkylation of diethyl acetamidomalonate (28.2B) Strecker synthesis (28.2) Enantioselective hydrogenation using a chiral catalyst (28.4)

15 smi97462_apps.qxd 12/6/04 1:09 PM Page A-15 APPENDIX G ow to Synthesize Particular Functional Groups A-15 Anhydrides eaction of an acid chloride with a carboxylate anion (22.8) Dehydration of a dicarboxylic acid (22.10) Aryl halides alogenation of benzene with X 2 + FeX 3 (18.3) eaction of a diazonium salt with ul, ubr, BF 4, NaI, or KI (25.14A) arboxylic acids xidative cleavage of an alkyne with ozone (12.11) xidation of a 1 alcohol with r 3 (or a similar r 6+ reagent), 2, 2 S 4 (12.12B) xidation of an alkyl benzene with KMn 4 (18.14A) xidation of an aldehyde (20.8) eaction of a Grignard reagent with 2 (20.14A) ydrolysis of a cyanohydrin (21.9) ydrolysis of an acid chloride (22.8) ydrolysis of an anhydride (22.9) ydrolysis of an ester (22.11) ydrolysis of an amide (22.13) ydrolysis of a nitrile (22.18A) Malonic ester synthesis (23.9) yanohydrins Addition of N to an aldehyde or ketone (21.9) 1,2-Diols Anti dihydroxylation of an alkene with a peroxyacid, followed by ring opening with or 2 (12.9A) Syn dihydroxylation of an alkene with KMn 4 or s 4 (12.9B) Enamines eaction of an aldehyde or ketone with a 2 amine (21.12) Epoxides Intramolecular S N 2 reaction of a halohydrin using base (9.6) Epoxidation of an alkene with mpba (12.8) Enantioselective epoxidation of an allylic alcohol with the Sharpless reagent (12.14) Esters S N 2 reaction of an alkyl halide with a carboxylate anion, (7.19) eaction of an acid chloride with an alcohol (22.8) eaction of an anhydride with an alcohol (22.9) Fischer esterification of a carboxylic acid with an alcohol (22.10) Ethers Williamson ether synthesis S N 2 reaction of an alkyl halide with an alkoxide, (9.6) eaction of an alkyl tosylate with an alkoxide, (9.13) Addition of an alcohol to an alkene in the presence of acid (10.12) alohydrins eaction of an epoxide with X (9.15) Addition of X and to an alkene (10.15) Imine eaction of an aldehyde or ketone with a 1 o amine (21.11)

16 smi97462_apps.qxd 12/6/04 1:09 PM Page A-16 A-16 APPENDIX G ow to Synthesize Particular Functional Groups Ketones ydration of an alkyne with 2, 2 S 4, and gs 4 (11.9) xidative cleavage of an alkene with 3 followed by Zn or ( 3 ) 2 S (12.10) xidation of a 2 o alcohol with any r 6+ reagent (12.12) Friedel rafts acylation (18.5) eaction of an acid chloride with an organocuprate reagent (20.13) ydrolysis of an imine or enamine (21.12) ydrolysis of an acetal (21.14B) eaction of a nitrile with a Grignard or organolithium reagent (22.18) Acetoacetic ester synthesis (23.10) Nitriles S N 2 reaction of an alkyl halide with NaN (7.19, 22.18) eaction of an aryl diazonium salt with un (25.14A) Phenols eaction of an aryl diazonium salt with 2 (25.14A)

17 smi97462_apps.qxd 12/6/04 1:09 PM Page A-17 Appendix eactions that Form arbon arbon Bonds Section eaction 11.11A S N 2 reaction of an alkyl halide with an acetylide anion, 11.11B pening of an epoxide ring with an acetylide anion, adical polymerization of an alkene Diels Alder reaction 18.5 Friedel rafts alkylation 18.5 Friedel rafts acylation eaction of an aldehyde or ketone with a Grignard or organolithium reagent 20.13A eaction of an acid chloride with a Grignard or organolithium reagent 20.13A eaction of an ester with a Grignard or organolithium reagent 20.13B eaction of an acid chloride with an organocuprate reagent 20.14A eaction of a Grignard reagent with B eaction of an epoxide with an organometallic reagent eaction of an α,β-unsaturated carbonyl compound with an organocuprate reagent 21.9 yanohydrin formation Wittig reaction to form an alkene S N 2 reaction of an alkyl halide with NaN eaction of a nitrile with a Grignard or organolithium reagent 23.8 Direct enolate alkylation using LDA and an alkyl halide 23.9 Malonic ester synthesis to form an α-substituted carboxylic acid Acetoacetic ester synthesis to form an α-substituted ketone 24.1 Aldol reaction to form a β-hydroxy carbonyl compound or an α,β-unsaturated carbonyl compound 24.2 rossed aldol reaction 24.3 Directed aldol reaction 24.5 laisen reaction to form a β-keto ester 24.6 rossed laisen reaction to form a β-dicarbonyl compound 24.7 Dieckmann reaction to form a five- or six-membered ring 24.8 Michael reaction to form a 1,5-dicarbonyl compound 24.9 obinson annulation to form a 2-cyclohexenone 27.10B Kiliani Fischer synthesis of an aldose 28.2B Alkylation of diethyl acetamidomalonate to form an amino acid 28.2 Strecker synthesis of an amino acid A-17

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