ROADMAP FOR REACTIONS Chapter 6 - Anslyn...
15
alcohols X 2 (B) X 2 /H 2 O (B) 1) BH 3 , 2) H 2 O 2 , NaOH (C, D) 1) Hg(OAc) 2 , H 2 O, 2) NaBH 4 , (A) H 3 O + /H 2 O (A) HX (A) H 2 /Pd, Pt,or Ni (D) vicinal dihaloalkanes halohydrins 1) OsO 4 (D), 2) NaHSO 3 vicinal diols aldehydes/ ketones alkenes alkanes 1) O 3 , 2) (CH 3 ) 2 S haloakanes ROADMAP FOR REACTIONS Chapter 6 Reactions that cleave carbon-carbon bonds are indicated by reagents that are circled. (A) (B) (C) (D) (E) (F) (G) (H) (I) (J) (K) (L) (M) (N) (O) 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° haloalkanes Stereochemistry: gives cis-alkenes as products Stereochemistry: gives trans-alkenes as products Reactivity of C–H bonds follows 3° > 2° > 1° Works for methyl, 1°, and 2° haloalkanes Works for 2° and 3° haloalkanes, may see rearrangements Works for all haloalkanes except methyl, although a bulky (non-nucleophilic) base must be used for 1° haloalkanes. 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 SOX 2 works for methyl, 1°, and 2° haloalkanes. HX can give rearrangements. For 1° alcohols For 2° alcohols Regiochemistry: the product with the more substituted alkene predominates
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Transcript of ROADMAP FOR REACTIONS Chapter 6 - Anslyn...
alcohols
X2
(B)
X2/
H2O
(B)
1) BH3, 2) H2O2, NaOH (C, D)
1) Hg(OAc)2, H2O, 2) NaBH4, (A)
H3O+/H2O (A)
HX
(A)
H2/Pd, Pt,or Ni (D)
vicinaldihaloalkanes
halohydrins
1) OsO4 (D), 2) NaHSO3 vicinaldiols
aldehydes/ketones
alkenesalkanes
1) O3, 2) (CH3)2S
haloakanes
ROADMAP FOR REACTIONS Chapter 6Reactions that cleave carbon-carbonbonds are indicated by reagentsthat are circled.
(A)(B)(C)(D)(E)(F)(G)(H)( I )(J)(K)
(L)
(M)(N)(O)
Regiochemistry: Markovnikov addition to a bondStereochemistry: anti-additionRegiochemistry: non-Markovnikov addition to a bondStereochemistry: syn-additionWorks well for methyl and 1° haloalkanesStereochemistry: gives cis-alkenes as productsStereochemistry: gives trans-alkenes as productsReactivity of C–H bonds follows 3° > 2° > 1°Works for methyl, 1°, and 2° haloalkanesWorks for 2° and 3° haloalkanes, may see rearrangementsWorks for all haloalkanes except methyl, although a bulky(non-nucleophilic) base must be used for 1° haloalkanes.Regiochemistry: follows Zaitzev’s rules so the more substitutedalkene predominates. Stereochemistry: requirement for theX and H to be eliminated with anti-periplanar geometry.PBr3 and SOX2 works for methyl, 1°, and 2° haloalkanes.HX can give rearrangements.For 1° alcoholsFor 2° alcoholsRegiochemistry: the product with the moresubstituted alkene predominates
Chapter 6Key:
Carbon-carbon bond formingreactions are indicated by reagentswritten with solid backgroundsand white lettering.
Reactions that cleave carbon-carbonbonds are indicated by reagentsthat are circled.
Chapter 7
ROADMAP FOR REACTIONS Chapters 6 7
alcohols
NaN
H2 /N
H3
Na /N
H3
(G)
2X2 1) (sia)2BH, 2) H2O2, NaOH (C)
1) BH3, 2) H2O2, NaOH
H2SO4, HgSO4 (A)
HX (A)
H2 /Lin
dlar Cat
. (F)
H2 /P
d, P
t, Ni vicinal
dihaloalkanes
halohydrins
vicinaldiols
geminaldihaloalkanes
vicinaltetrahaloalkanes
aldehydes/ketones
alkenesalkanes
CR
(E)
NaC
alkynes
haloakanes
X2
(B)
X2/H
2O (B
)
1) BH3, 2) H2O2, NaOH (C, D)
1) Hg(OAc)2, H2O, 2) NaBH4, (A)
H3O+/H2O (A)
HX
(A)
H2/Pd, Pt,or Ni (D)
1) OsO4 (D), 2) NaHSO3
1) O3, 2) (CH3)2S
allylichalides
alcohols
RC
NaN
H2
/NH
3
Na
/NH
3 (G
)
2X2 1) (sia)2BH, 2) H2O2, NaOH (C)
1) BH3, 2) H2O2, NaOH
H2SO4, HgSO4 (A)
HX (A)
H2
/Lin
dlar
Cat
. (F)
H2
/Pd,
Pt,
Ni
X2 (
B)
X2/
H2O
(B)
1) BH3, 2) H2O2, NaOH (C, D)
1) Hg(OAc)2, H2O, 2) NaBH4, (A)
H3O+/H2O (A)
X2, hv or heat (H)
HX
(A)
H2/Pd, Pt,or Ni (D)
HB
r, pe
roxi
des
(C)
NBS (O)
Chapter 6Key:
Carbon-carbon bond formingreactions are indicated by reagentswritten with solid backgroundsand white lettering.
Reactions that cleave carbon-carbonbonds are indicated by reagentsthat are circled.
Chapter 7
Chapter 8
vicinaldihaloalkanes
halohydrins
1) OsO4 (D), 2) NaHSO3 vicinaldiols
geminaldihaloalkanes
vicinaltetrahaloalkanes
aldehydes/ketones
alkenesalkanes
CR
(E)
NaC
alkynes
1) O3, 2) (CH3)2S
haloakanes
ROADMAP FOR REACTIONS Chapters 6 7 8
(A)(B)(C)(D)(E)(F)(G)(H)( I )(J)(K)
(L)
(M)(N)(O)
Regiochemistry: Markovnikov addition to a bondStereochemistry: anti-additionRegiochemistry: non-Markovnikov addition to a bondStereochemistry: syn-additionWorks well for methyl and 1° haloalkanesStereochemistry: gives cis-alkenes as productsStereochemistry: gives trans-alkenes as productsReactivity of C–H bonds follows 3° > 2° > 1°Works for methyl, 1°, and 2° haloalkanesWorks for 2° and 3° haloalkanes, may see rearrangementsWorks for all haloalkanes except methyl, although a bulky(non-nucleophilic) base must be used for 1° haloalkanes.Regiochemistry: follows Zaitzev’s rules so the more substitutedalkene predominates. Stereochemistry: requirement for theX and H to be eliminated with anti-periplanar geometry.PBr3 and SOX2 works for methyl, 1°, and 2° haloalkanes.HX can give rearrangements.For 1° alcoholsFor 2° alcoholsRegiochemistry: the product with the more substituted alkenepredominates
allylichalides
alcohols
NaC
N (I
)
CLi
(E)
RC
NaH
R2
(I)
NaN
3 (I
)
NaS
R (I
)
NaS
H (I
)
NaO
H (E
)
H2O
, aci
d (J
)
NaO
R (E
)
HO
R, a
cid
(J)
NaN
H2
/NH
3
Na
/NH
3 (G
)
2X2 1) (sia)2BH, 2) H2O2, NaOH (C)
1) BH3, 2) H2O2, NaOH
H2SO4, HgSO4 (A)
HX (A)
H2
/Lin
dlar
Cat
. (F)
H2
/Pd,
Pt,
Ni
X2
(B)
X2/
H2O
(B)
1) BH3, 2) H2O2, NaOH (C, D)
1) Hg(OAc)2, H2O, 2) NaBH4, (A)
H3O+/H2O (A)
X2, hv or heat (H)
HX
(A)
H2/Pd, Pt,or Ni (D)
NaO
R (K
)
HB
r, pe
roxi
des
(C)
NBS (O)
Chapter 6Key:
Carbon-carbon bond formingreactions are indicated by reagentswritten with solid backgroundsand white lettering.
Reactions that cleave carbon-carbonbonds are indicated by reagentsthat are circled.
Chapter 7
Chapter 8
Chapter 9
vicinaldihaloalkanes
halohydrins
1) OsO4 (D), 2) NaHSO3 vicinaldiols
geminaldihaloalkanes
vicinaltetrahaloalkanes
aldehydes/ketones
alkenes
alkylazidesaminesnitriles thioethersthiols
alkanes
CR
(E)
NaC
alkynes
1) O3, 2) (CH3)2S
haloakanes
ethers
ROADMAP FOR REACTIONS Chapters 6 7 8 9
allylichalides
alcohols
NaC
N (
I)
CLi
(E)
RC
NaH
R2
(I)
NaN
3 (I
)
NaS
R (I
)
NaS
H (I
)
NaO
H (E
)
H2O
, aci
d (J
)
NaO
R (E
)
HO
R, a
cid
(J)
NaN
H2
/NH
3
Na
/NH
3 (G
)
H2C
rO4 (N
)
HIO
4 H
X o
r PB
r 3 o
r SO
Cl 2
(L)
H3PO4
H2C
rO4
PCC
(M)
2X2 1) (sia)2BH, 2) H2O2, NaOH (C)
1) BH3, 2) H2O2, NaOH
H2SO4, HgSO4 (A)
HX (A)
H2
/Lin
dlar
Cat
. (F)
H2
/Pd,
Pt,
Ni
X2
(B)
X2/
H2O
(B)
1) BH3, 2) H2O2, NaOH (C, D)
1) Hg(OAc)2, H2O, 2) NaBH4, (A)
H3O+/H2O (A)
X2, hv or heat (H)
HX
(A)
H2/Pd, Pt,or Ni (D)
NaO
R (K
)
HB
r, pe
roxi
des
(C)
NBS (O)
Chapter 6Key:
Carbon-carbon bond formingreactions are indicated by reagentswritten with solid backgrounds and white lettering.Reactions that cleave carbon-carbonbonds are indicated by reagentsthat are circled.
Chapter 7Chapter 8Chapter 9Chapter 10
vicinaldihaloalkanes
halohydrins
1) OsO4 (D), 2) NaHSO3 vicinaldiols
carboxylicacids
geminaldihaloalkanes
vicinaltetrahaloalkanes
aldehydes/ketones
alkenes
alkylazidesaminesnitriles thioethersthiols
alkanes
CR
(E)
NaC
alkynes
1) O3, 2) (CH3)2S
haloakanes
ethers
ROADMAP FOR REACTIONS Chapters 6 7 8 9 10
Chapter 6Key:
Carbon-carbon bond formingreactions are indicated by reagentswritten with solid backgrounds and white lettering.
Reactions that cleave carbon-carbonbonds are indicated by reagentsthat are circled.
Chapter 7Chapter 8Chapter 9Chapter 10Chapter 11
ROADMAP FOR REACTIONS Chapters 6 7 8 9 10 11
allylichalides
alcohols
NaC
N (I
)
CLi (
E)RC
NaH
R2
(I)
NaN
3 (I
)
NaS
R (I
)
NaS
H (I
)
NaO
H (E
)
H2O
, acid
(J)
NaO
R (E
)
HOR
, acid
(J)
NaN
H2 /N
H3
Na /N
H3
(G)
H2C
rO4
(N)
HIO
4 HX
or P
Br 3
or SOCl 2
(L)
H3PO4
H2C
rO4
PCC
(M)
2X2 1) (sia)2BH, 2) H2O2, NaOH (C)
1) BH3, 2) H2O2, NaOH
H2SO4, HgSO4 (A)
HX (A)
H2 /Lin
dlar Cat
. (F)
H2 /P
d, P
t, Ni
X2
(B)
X2/H
2O (B
)
1) BH3, 2) H2O2, NaOH (C, D)
1) Hg(OAc)2, H2O, 2) NaBH4, (A)
H3O+/H2O (A)
H3O+/H2O
X2, hv or heat (H)
HX
(A)
H2/Pd, Pt,or Ni (D)
NaO
R (K
)
HBr,
perox
ides
(C)
NBS (O)
vicinaldihaloalkanes
halohydrins
1) OsO4 (D), 2) NaHSO3 vicinaldiols
epoxides
silylethers
carboxylicacids
vicinalaminoalcohols
geminaldihaloalkanes
vicinaltetrahaloalkanes
aldehydes/ketones
alkenes
alkylazidesaminesnitriles thioethersthiols
HI
ROH/acid (J)
1) Cl2, H2O, 2) NaOH, H2O
1) LiA
lH4
2) H
2Ot-
BuMe 3SiC
l/pyridine
m-CBPA
alkanes
CR
(E)
NaC
alkynes
1) O3, 2) (CH3)2S
haloakanes
ethers
NH
3
ROADMAP FOR REACTIONSCarbon-carbon bond formingreactions are indicated byreagents written with solidbackgrounds and white lettering.
Chapter 15
cyclopropanes
geminal dihalocyclopropanes
alkenes
haloalkanes alcohols
CHX3(CH3)3COK
1) Mg, 2) , 3) H3O+/H2O
CH2I2Zn (Cu)
R2CuLi
O
(A)(B)(C)(D)(E)(F)(G)(H)( I )(J)(K)
(L)
(M)(N)(O)
Regiochemistry: Markovnikov addition to a bondStereochemistry: anti-additionRegiochemistry: non-Markovnikov addition to a bondStereochemistry: syn-additionWorks well for methyl and 1° haloalkanesStereochemistry: gives cis-alkenes as productsStereochemistry: gives trans-alkenes as productsReactivity of C–H bonds follows 3° > 2° > 1°Works for methyl, 1°, and 2° haloalkanesWorks for 2° and 3° haloalkanes, may see rearrangementsWorks for all haloalkanes except methyl, although a bulky(non-nucleophilic) base must be used for 1° haloalkanes.Regiochemistry: follows Zaitzev’s rules so the more substitutedalkene predominates. Stereochemistry: requirement for theX and H to be eliminated with anti-periplanar geometry.PBr3 and SOX2 works for methyl, 1°, and 2° haloalkanes.HX can give rearrangements.For 1° alcoholsFor 2° alcoholsRegiochemistry: the product with the more substituted alkenepredominates
vinyl halides
ROADMAP FOR REACTIONS
Key:Chapter 15
Carbon-carbon bond formingreactions are indicated byreagents written with solidbackgrounds and white lettering.
Chapter 16
Chapters 15 16H
3O+ /H
2O
Br 2
, aci
d
H3O+/H2O
RO
H/H
+
ROH/H+
cyclopropanes
geminal dihalocyclopropanes
acetals
aldehydes/ketones
alkenes
haloalkanes alcohols
CHX3(CH3)3COK
1) Mg, 2) , 3) H3O+/H2O
CH2I2Zn (Cu)
1) RC2) H3O+/H2O
CNa
O
1) R
MgX
, 2)
H3O
+Ph3P
+C
R2–
1) R
Li,
2) H
3O+
1) N
aBH
2, 2
) H3O
+
N2H4, KOH
amin
e, N
aBH
3CN
R2N
H
RN
H2
Zn (Hg), HCl
Pt, H
2
hemiacetals
, -unsaturatedesters
-haloketones -hydroxyalkynes cyanohydrins
alkanes
imines
enamines
amines
1) NaCN2) H2O(MeO)2P
1)
2) BaseCH2C
O
OEt
O
R2CuLivinyl halides
ROADMAP FOR REACTIONS
Key:Chapter 15
Carbon-carbon bond formingreactions are indicated byreagents written with solidbackgrounds and white lettering.
Chapter 16
Chapter 17
Chapters 15 16 17H
3O+ /H
2O
Br 2
, aci
d
H3O+/H2O
SOC
l 2
CH2N2
1) LiAlH4, 2) H3O+/H2O
ROH acid
RO
H/H
+
ROH/H+
cyclopropanes
geminal dihalocyclopropanes
acetals
aldehydes/ketones
alkenes
carboxylic acids
esters
haloalkanes
acid chlorides
alcohols
CHX3(CH3)3COK
1) Mg, 2) , 3) H3O+/H2O
CH2I2Zn (Cu)
1) RC2) H3O+/H2O
CNa
1) Mg2) CO23) H3O+/H2O
R2CuLi
O
1) R
MgX
, 2)
H3O
+Ph3P
+C
R2–
1) R
Li,
2) H
3O+
1) N
aBH
2, 2
) H3O
+
N2H4, KOH
amin
e, N
aBH
3CN
R2N
H
RN
H2
Zn (Hg), HCl
Pt, H
2
hemiacetals
, -unsaturatedesters
-haloketones -hydroxyalkynes cyanohydrins
alkanes
imines
enamines
amines
1) NaCN2) H2O(MeO)2P
1)
2) BaseCH2C
O
OEt
O
vinyl halides
ROADMAP FOR REACTIONS
Key:Chapter 15
Carbon-carbon bond formingreactions are indicated byreagents written with solidbackgrounds and white lettering.
Chapter 16
Chapter 17
Chapter 18
Chapters 15 16 17 18H
3O+ /H
2O
Br 2
, aci
d
H3O+/H2O
SOC
l 2
CH2N2
1) LiAlH4, 2) H3O+/H2O
1) LiAlH4, 2) H3O+/H2O
1) LiAlH4, 2) H3O+/H2O
1) L
iAlH
4, 2
) H3O
+ /H2O
1) D
IBA
L, 2
) H3O
+
H2O acid or base
H2O acid or base
H2O acid or base
ROH acid
RCO2H
H2O
H2O ROH
ROH
RO
H/H
+
ROH/H+
cyclopropanes
geminal dihalocyclopropanes
acetals
aldehydes/ketones
alkenes
carboxylic acids
esters
haloalkanes
acid chloridesNHR2
NHR2
NH
R2
acidanhydrides
nitriles
amides
alcohols
CHX3(CH3)3COK
1) Mg, 2) , 3) H3O+/H2O
CH2I2Zn (Cu)
1) RC2) H3O+/H2O
CNa
1) Mg2) CO23) H3O+/H2O
R2CuLi
O
1) R
MgX
, 2)
H3O
+
1) R
2CuL
i, 2
) H2O
1) 2
RM
gX,
2) H
2O
Ph3P
+C
R2–
1) R
Li,
2) H
3O+
1) N
aBH
2, 2
) H3O
+
N2H4, KOH
amin
e, N
aBH
3CN
R2N
H
RN
H2
Zn (Hg), HCl
Pt, H
2
hemiacetals
, -unsaturatedesters
-haloketones -hydroxyalkynes cyanohydrins
alkanes
imines
enamines
amines
1) NaCN2) H2O(MeO)2P
1)
2) BaseCH2C
O
OEt
O
vinyl halides
Carbon-carbon bond formingreactions are indicated byreagents written with solidbackgrounds and white lettering.
ROADMAP FOR REACTIONS
H3O+R3
R2R1 O
R4HONaOR/HOR
Aldol Reaction
various enolatesor amines
Michael Reaction
1) R2CuLi2) H3O+/H2O
1) 2°-amine2) acid chloride3) H3O+/H2O
1) NaOEt/HOEt2) H3O+/H2O
1) LDA2) R-X3) H3O+/H2O
1) 2°-amine2) R-X3) H3O+/H2O
ketones,aldehydes
-Hydroxy carbonyls
ClaisenCondensation
esters
-ketoesters
1) NaOEt/HOEt2) H3O+/H2O
R4 R5
R3
R1
R6
R7
R8R2
OO
O
DieckmannCondensation
diesters
cyclic -ketoesters
1) NaOEt/HOEt2) R-X3) NaOH, H2O4) H3O+/H2O5)
1) NaOEt/HOEt2) R-X3) NaOH, H2O4) H3O+/H2O5)
Malonic EsterSynthesis
malonicesters
alkylated carboxylic acids
Acetoacetic EsterSythesis
acetoaceticesters
alylated methyl ketones
R3R2
R1
O
R4
O
OH
OH
R1
O
R1
R2
O
H3C
H3C
R1
O
R1
R2
Alkylated -carbons
R3
R2
R1
O
R4
, -Unsaturated carbonyls
-Alkylated carbonyls
R2
R3
R4
R1
O
Nu
Nu = enolate formingspecies or amines
R2
R3
R4
R1 R5
O
Chapter 19
R2 R3
R1 R4
O O
R2 R3
OR4R1
O O
-Dicarbonyls
ROADMAP FOR REACTIONSCarbon-carbon bond formingreactions are indicated by reagentswritten with solid backgroundsand white lettering.
HX
alkene
dienes
cyclohexenes
allylic halides
Chapter 20
ROADMAP FOR REACTIONS
H2CrO4
H2CrO4NBS
carboxyphenolsquinones
aryl carboxylicacids
benzylicbromides
Chapter 20Key:
Carbon-carbon bond formingreactions are indicated by reagentswritten with solid backgroundsand white lettering.
Chapter 21
HX
alkene
dienes
cyclohexenes
allylic halides
Chapters 20 21
alkylbenzenes
phenols1) NaOH2) CO23) H3O+/H2O
ROADMAP FOR REACTIONS
H2CrO4
H2CrO4NBS
NaO
H, H
2O
H2,
Ni
HNO3, H2SO4
H2SO4, SO3
1) F
e, H
Cl
2) N
aOH
phenols
carboxyphenolsquinones
anilines
nitrobenzenes
aryl carboxylicacids
benzylicbromides
1) NaOH2) CO23) H3O+/H2O
Chapter 20Key:
Carbon-carbon bond formingreactions are indicated by reagentswritten with solid backgroundsand white lettering.
Chapter 21
Chapter 22
sulfobenzenes
acyl benzenes
aryl rings
HX
alkene
R(CO)X, AlX3
dienes
cyclohexenes
allylic halides
Chapters 20 21 22
RX
, AlX
3
3°-R
OH
, H3P
O4
H3PO4
NaNH2, NH3
X2, FeX3
alkylbenzenes
halobenzenes
ROADMAP FOR REACTIONS
H2O
H2CrO4
H2CrO4NBS
NaO
H, H
2O
H2,
Ni
HNO3, H2SO4
H2SO4, SO3
1) F
e, H
Cl
2) N
aOH
phenols
carboxyphenolsquinones
H3P
O2
1) HNO2, 2) HClanilines
nitrobenzenes
alkylbenzenes
aryl carboxylicacids
benzylicbromides
halobenzenes
1) KN3, 2) H2O,3) LiAlH4, 4) H3O+/H2O
1) NaOH2) CO23) H3O+/H2O
1) e
xces
s M
el2)
NaO
H, h
eat
1) H
2O2,
2) h
eat
Chapter 20Key:
Carbon-carbon bond formingreactions are indicated by reagentswritten with solid backgroundsand white lettering.
Chapter 21
Chapter 22
Chapter 23
epoxides
HB
F 4
vicinal aminoalcohols
aryl !uorides
aryl nitriles
sulfobenzenes
acyl benzenes
KIaryl iodides
aryl rings
ketones
HX
alkene
KCN, CaCN
R(CO)X, AlX3
dienes
aryldiazonium
salts
cyclohexenes
amines
alkenes
allylic halides
Chapters 20 21 22 23
RX
, AlX
3
3°-R
OH
, H3P
O4
H3PO4
HNO2
NaNH2, NH3
X2, FeX3
![SECTION I HALOAKANES · substrate i.e. haloalkane and the reaction is of the first order change i.e. Rate ∝ [substrate] or Rate = [R-X] (ii) This type of reaction proceeds in TWO](https://static.fdocuments.net/doc/165x107/5e335ee10bda0141800364ce/section-i-haloakanes-substrate-ie-haloalkane-and-the-reaction-is-of-the-first.jpg)
