ROADMAP FOR REACTIONS Chapter 6
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1 RADMAP FR REACTINS Chapter 6 (A) (B) (C) (D) (E) (F) (G) (H) (I) (J) (K) (L) (M) (N) () Regiochemistry: Markovnikov addition to a bond Stereochemistry: anti-addition Regiochemistry: non-markovnikov addition to a bond Stereochemistry: syn-addition Works well for methyl and 1 halo Stereochemistry: gives cis- as products Stereochemistry: gives trans- as products Reactivity of C H bonds follows 3 > 2 > 1 Works for methyl, 1, and 2 halo Works for 2 and 3 halo, may see rearrangements Works for all halo except methyl, although a bulky (non-nucleophilic) base must be used for 1 halo. Regiochemistry: follows Zaitzev s rules so the more substituted alkene predominates. Stereochemistry: requirement for the X and H to be eliminated with anti-periplanar geometry. PBr 3 and SX 2 works for methyl, 1, and 2 halo. HX can give rearrangements. For 1 For 2 Regiochemistry: the product with the more substituted alkene predominates Reactions that cleave carbon-carbon bonds are indicated by reagents that are circled. halohydrins 1) 3, 2) (CH 3 ) 2 S X 2 /H 2 (B) X 2 (B) 1) s 4 (D), 2) NaHS 3 diols 1) BH 3, 2) H 2 2, NaH (C, D) H 2 /Pd, Pt,or Ni (D) H 3 + /H 2 (A) 1) Hg(Ac) 2, H 2, 2) NaBH 4, (A) haloakanes
2 RADMAP FR REACTINS Chapters 6 7 Chapter 6 Chapter 7 geminal tetrahalo Reactions that cleave carbon-carbon bonds are indicated by reagents that are circled. 2X 2 1) (sia)2 BH, 2) H 2 2, NaH (C) alkynes 1) BH 3, 2) H 2 2, NaH H 2 S 4, HgS 4 (A) CR (E) NaC H 2 /Pd, Pt, Ni Na /NH 3 (G) NaNH 2 /NH 3 H 2 /Lindlar Cat. (F) halohydrins 1) 3, 2) (CH 3 ) 2 S X 2 /H 2 (B) X 2 (B) 1) s 4 (D), 2) NaHS 3 diols 1) BH 3, 2) H 2 2, NaH (C, D) H 2 /Pd, Pt,or Ni (D) H 3 + /H 2 (A) 1) Hg(Ac) 2, H 2, 2) NaBH 4, (A) haloakanes
3 RADMAP FR REACTINS Chapters Chapter 6 Chapter 7 Chapter 8 geminal tetrahalo Reactions that cleave carbon-carbon bonds are indicated by reagents that are circled. 2X 2 1) (sia)2 BH, 2) H 2 2, NaH (C) alkynes 1) BH 3, 2) H 2 2, NaH H 2 S 4, HgS 4 (A) RC CR (E) NaC H 2 /Pd, Pt, Ni Na /NH 3 (G) NaNH 2 /NH 3 H 2 /Lindlar Cat. (F) halohydrins 1) 3, 2) (CH 3 ) 2 S X 2 /H 2 (B) X 2 (B) 1) s 4 (D), 2) NaHS 3 diols 1) BH 3, 2) H 2 2, NaH (C, D) H 2 /Pd, Pt,or Ni (D) H 3 + /H 2 (A) 1) Hg(Ac) 2, H 2, 2) NaBH 4, (A) NBS () allylic halides X 2, hv or heat (H) HBr, peroxides (C) haloakanes (A) (B) (C) (D) (E) (F) (G) (H) (I) (J) (K) (L) (M) (N) () Regiochemistry: Markovnikov addition to a bond Stereochemistry: anti-addition Regiochemistry: non-markovnikov addition to a bond Stereochemistry: syn-addition Works well for methyl and 1 halo Stereochemistry: gives cis- as products Stereochemistry: gives trans- as products Reactivity of C H bonds follows 3 > 2 > 1 Works for methyl, 1, and 2 halo Works for 2 and 3 halo, may see rearrangements Works for all halo except methyl, although a bulky (non-nucleophilic) base must be used for 1 halo. Regiochemistry: follows Zaitzev s rules so the more substituted alkene predominates. Stereochemistry: requirement for the X and H to be eliminated with anti-periplanar geometry. PBr 3 and SX 2 works for methyl, 1, and 2 halo. HX can give rearrangements. For 1 For 2 Regiochemistry: the product with the more substituted alkene predominates
4 RADMAP FR REACTINS Chapters geminal tetrahalo Chapter 6 Chapter 7 Chapter 8 Chapter 9 Reactions that cleave carbon-carbon bonds are indicated by reagents that are circled. 2X 2 1) (sia)2 BH, 2) H 2 2, NaH (C) alkynes 1) BH 3, 2) H 2 2, NaH H 2 S 4, HgS 4 (A) CLi (E) RC CR (E) NaC H 2 /Pd, Pt, Ni allylic halides NaCN (I) NaSH (I) Na /NH 3 (G) H 2 /Lindlar Cat. (F) NaSR (I) NaHR 2 (I) NaN 3 (I) NaNH 2 /NH 3 halohydrins 1) 3, 2) (CH 3 ) 2 S X 2 /H 2 (B) X 2 (B) 1) s 4 (D), 2) NaHS 3 diols 1) BH 3, 2) H 2 2, NaH (C, D) H 2 /Pd, Pt,or Ni (D) H 3 + /H 2 (A) 1) Hg(Ac) 2, H 2, 2) NaBH 4, (A) NBS () X 2, hv or heat (H) HBr, peroxides (C) NaR (K) NaR (E) ethers HR, acid (J) NaH (E) H 2, acid (J) haloakanes nitriles thiols thioethers amines alkyl azides
5 RADMAP FR REACTINS Chapters geminal tetrahalo Chapter 6 Chapter 7 Chapter 8 Chapter 9 Chapter 10 Reactions that cleave carbon-carbon bonds are indicated by reagents that are circled. 2X 2 1) (sia)2 BH, 2) H 2 2, NaH (C) alkynes 1) BH 3, 2) H 2 2, NaH H 2 S 4, HgS 4 (A) CLi (E) RC CR (E) NaC H 2 /Pd, Pt, Ni Na /NH 3 (G) H 2 /Lindlar Cat. (F) allylic halides X 2, hv or heat (H) halohydrins H 2 /Pd, Pt,or Ni (D) NBS () X 2 /H 2 (B) HBr, peroxides (C) NaNH 2 /NH 3 X 2 (B) NaR (K) 1) 3, 2) (CH 3 ) 2 S 1) s 4 (D), 2) NaHS 3 diols 1) BH 3, 2) H 2 2, NaH (C, D) H 3 + /H 2 (A) 1) Hg(Ac) 2, H 2, 2) NaBH 4, (A) H 3 P 4 NaR (E) ethers HR, acid (J) NaH (E) HI 4 H 2, acid (J) H 2 Cr 4 (N) HX or PBr 3 or SCl 2 (L) H 2 Cr 4 PCC (M) haloakanes NaCN (I) NaSH (I) NaSR (I) NaHR 2 (I) NaN 3 (I) carboxylic acids nitriles thiols thioethers amines alkyl azides
6 RADMAP FR REACTINS Chapters geminal tetrahalo Chapter 6 Chapter 7 Chapter 8 Chapter 9 Chapter 10 Chapter 11 Reactions that cleave carbon-carbon bonds are indicated by reagents that are circled. 2X 2 1) (sia)2 BH, 2) H 2 2, NaH (C) alkynes 1) BH 3, 2) H 2 2, NaH H 2 S 4, HgS 4 (A) CLi (E) RC CR (E) NaC H 2 /Pd, Pt, Ni Na /NH 3 (G) H 2 /Lindlar Cat. (F) allylic halides X 2, hv or heat (H) halohydrins H 2 /Pd, Pt,or Ni (D) NBS () X 2 /H 2 (B) HBr, peroxides (C) NaNH 2 /NH 3 X 2 (B) NaR (K) haloakanes 1) 3, 2) (CH 3 ) 2 S 1) s 4 (D), 2) NaHS 3 diols 1) Cl 2, H 2, 2) NaH, H 2 m-cbpa 1) BH 3, 2) H 2 2, NaH (C, D) H 3 + /H 2 (A) 1) Hg(Ac) 2, H 2, 2) NaBH 4, (A) RH/acid (J) HI H 3 P 4 ethers NaR (E) HR, acid (J) NaH (E) HI 4 H 2, acid (J) H 2 Cr 4 (N) HX or PBr 3 or SCl 2 (L) H 2 Cr 4 PCC (M) amino H 3 + /H 2 NH 3 epoxides 1) LiAlH 4 2) H 2 t-bume 3 SiCl/pyridine silyl ethers NaCN (I) NaSH (I) NaSR (I) NaHR 2 (I) NaN 3 (I) carboxylic acids nitriles thiols thioethers amines alkyl azides
7 RADMAP FR REACTINS Chapter 15 reactions are indicated by reagents written with solid backgrounds geminal dihalo CHX 3 (CH 3 ) 3 CK CH 2 I 2 Zn (Cu) vinyl halides R 2 CuLi halo 1) Mg, 2), 3) H 3 + /H 2 (A) (B) (C) (D) (E) (F) (G) (H) (I) (J) (K) (L) (M) (N) () Regiochemistry: Markovnikov addition to a bond Stereochemistry: anti-addition Regiochemistry: non-markovnikov addition to a bond Stereochemistry: syn-addition Works well for methyl and 1 halo Stereochemistry: gives cis- as products Stereochemistry: gives trans- as products Reactivity of C H bonds follows 3 > 2 > 1 Works for methyl, 1, and 2 halo Works for 2 and 3 halo, may see rearrangements Works for all halo except methyl, although a bulky (non-nucleophilic) base must be used for 1 halo. Regiochemistry: follows Zaitzev s rules so the more substituted alkene predominates. Stereochemistry: requirement for the X and H to be eliminated with anti-periplanar geometry. PBr 3 and SX 2 works for methyl, 1, and 2 halo. HX can give rearrangements. For 1 For 2 Regiochemistry: the product with the more substituted alkene predominates
8 RADMAP FR REACTINS Chapters reactions are indicated by reagents written with solid backgrounds acetals, -unsaturated -halo -hydroxyalkynes cyanohydrins Chapter 15 Chapter 16 H 3 + /H 2 RH/H + hemiacetals 1) (Me) 2 P CH 2 C 2) Base RH/H + H 3 + /H 2 Et Br 2, acid 1) RC CNa 2) H 3 + /H 2 1) NaCN 2) H 2 Zn (Hg), HCl N 2 H 4, KH geminal dihalo CHX 3 (CH 3 ) 3 CK CH 2 I 2 Zn (Cu) Ph 3 P + CR 2 1) RMgX, 2) H 3 + 1) RLi, 2) H 3 + 1) NaBH 2, 2) H 3 + Pt, H 2 RNH 2 imines R 2 NH enamines amine, NaBH 3 CN vinyl halides R 2 CuLi amines halo 1) Mg, 2), 3) H 3 + /H 2
9 RADMAP FR REACTINS Chapters acetals H 3 + /H 2 RH/H + hemiacetals 1), -unsaturated (Me) 2 P 2) Base RH/H + H 3 + /H 2 CH 2 C Et -halo -hydroxyalkynes cyanohydrins Br 2, acid 1) RC CNa 2) H 3 + /H 2 1) NaCN 2) H 2 Zn (Hg), HCl N 2 H 4, KH reactions are indicated by reagents written with solid backgrounds Chapter 15 Chapter 16 Chapter 17 geminal dihalo CHX 3 (CH 3 ) 3 CK CH 2 I 2 Zn (Cu) Ph 3 P + CR 2 1) RMgX, 2) H 3 + R 2 CuLi halo 1) Mg 2) C 2 3) H 3 + /H 2 1) Mg, 2), 3) H 3 + /H 2 1) LiAlH 4, 2) H 3 + /H 2 carboxylic acids CH 2 N 2 RH acid SCl 2 1) RLi, 2) H 3 + 1) NaBH 2, 2) H 3 + Pt, H 2 RNH 2 imines R 2 NH enamines amine, NaBH 3 CN vinyl halides amines acid chlorides
10 RADMAP FR REACTINS Chapters acetals H 3 + /H 2 RH/H + hemiacetals 1), -unsaturated (Me) 2 P 2) Base RH/H + H 3 + /H 2 CH 2 C Et -halo -hydroxyalkynes cyanohydrins Br 2, acid 1) RC CNa 2) H 3 + /H 2 1) NaCN 2) H 2 Zn (Hg), HCl N 2 H 4, KH reactions are indicated by reagents written with solid backgrounds Chapter 15 Chapter 16 Chapter 17 Chapter 18 geminal dihalo CHX 3 (CH 3 ) 3 CK CH 2 I 2 Zn (Cu) Ph 3 P + CR 2 1) RMgX, 2) H 3 + 1) RLi, 2) H 3 + SCl 2 1) NaBH 2, 2) H 3 + Pt, H 2 1) DIBAL, 2) H 3 + RNH 2 halo 1) Mg 2) C 2 3) H 3 + /H 2 carboxylic acids R 2 CuLi 1) Mg, 2), 3) H 3 + /H 2 1) LiAlH 4, 2) H 3 + /H 2 H 2 acid or base CH 2 N 2 RH acid H 2 RH RH H 2 1) LiAlH 4, 2) H 3 + /H 2 NHR 2 imines R 2 NH enamines amine, NaBH 3 CN 1) R 2 CuLi, 2) H 2 vinyl halides 1) 2RMgX, 2) H 2 amines acid chlorides RC 2 H acid anhydrides NHR 2 amides 1) LiAlH 4, 2) H 3 + /H 2 NHR 2 H 2 acid or base H 2 acid or base nitriles 1) LiAlH 4, 2) H 3 + /H 2
11 RADMAP FR REACTINS, aldehydes Chapter 19 reactions are indicated by reagents written with solid backgrounds Aldol Reaction NaR/HR -Hydroxy carbonyls R 3 H R 4 R 2 H 3 +, -Unsaturated carbonyls R 3 R 4 R 2 1) LDA 2) R-X 3) H 3 + /H 2 1) 2 -amine 2) R-X 3) H 3 + /H 2 Alkylated -carbons R 4 R 3 R 2 1) R 2 CuLi 2) H 3 + /H 2 -Alkylated carbonyls R 2 R 5 R 3 R 4 1) 2 -amine 2) acid chloride 3) H 3 + /H 2 -Dicarbonyls R 4 R 2 R 3 Michael Reaction various enolates or amines R 2 Nu R 3 R 4 Nu = enolate forming species or amines di malonic acetoacetic Claisen Condensation Dieckmann Condensation Malonic Ester Synthesis Acetoacetic Ester Sythesis 1) NaEt/HEt 2) H 3 + /H 2 1) NaEt/HEt 2) H 3 + /H 2 1) NaEt/HEt 2) R-X 3) NaH, H 2 4) H 3 + /H 2 5) 1) NaEt/HEt 2) R-X 3) NaH, H 2 4) H 3 + /H 2 5) -keto cyclic -keto alkylated carboxylic acids alylated methyl R 2 R 3 R 4 R 2 R 8 R 7 H H 3 C R 3 R 6 R 4 R 5 H R 2 H 3 C R 2
12 RADMAP FR REACTINS Chapter 20 dienes alkene HX cyclohexenes allylic halides
13 RADMAP FR REACTINS Chapters Chapter 20 Chapter 21 alkene cyclohexenes dienes HX allylic halides quinones H 2 Cr 4 phenols 1) NaH 2) C 2 3) H 3 + /H 2 carboxy phenols benzylic bromides NBS alkyl benzenes H 2 Cr 4 aryl carboxylic acids
14 RADMAP FR REACTINS Chapters Chapter 20 Chapter 21 Chapter 22 alkene cyclohexenes dienes HX allylic halides quinones H 2 Cr 4 phenols 1) NaH 2) C 2 3) H 3 + /H 2 carboxy phenols benzylic bromides NBS alkyl benzenes H 2 Cr 4 aryl carboxylic acids H 3 P 4 3 -RH, H 3 P 4 RX, AlX 3 NaH, H 2 sulfobenzenes H 2 S 4, S 3 aryl rings acyl benzenes R(C)X, AlX 3 HN 3, H 2 S 4 nitrobenzenes 1) Fe, HCl 2) NaH H 2, Ni X 2, FeX 3 halobenzenes anilines NaNH 2, NH 3
15 RADMAP FR REACTINS Chapters dienes alkene HX cyclohexenes allylic halides Chapter 20 Chapter 21 Chapter 22 Chapter 23 quinones H 2 Cr 4 phenols 1) NaH 2) C 2 3) H 3 + /H 2 carboxy phenols benzylic bromides NBS alkyl benzenes H 2 Cr 4 aryl carboxylic acids H 3 P 4 3 -RH, H 3 P 4 RX, AlX 3 NaH, H 2 sulfobenzenes H 2 S 4, S 3 X 2, FeX 3 halobenzenes aryl rings acyl benzenes R(C)X, AlX 3 HN 3, H 2 S 4 nitrobenzenes H 3 P 2 1) Fe, HCl 2) NaH H 2, Ni aryl nitriles H 2 KCN, CaCN aryl diazonium salts 1) HN 2, 2) HCl KI anilines aryl iodides NaNH 2, NH 3 amines epoxides 1) KN 3, 2) H 2, 3) LiAlH 4, 4) H 3 + /H 2 HBF 4 aryl fluorides amino HN 2 1) excess Mel 2) NaH, heat 1) H 2 2, 2) heat
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