最新有机化学常见官能团的反应总结.docx
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最新有机化学常见官能团的反应总结
FunctionalGroupInterconversion
C-H
1-a
bc
d
C-OHC-X
C-NH2
C-S
C-OR
2-a
bc
C-OH
C-（OR）2
C（O）OR
C-OH
3-a
bc
d
C-HC-ORC-X
C-NH2
C-N
4-a
b
cd
C-H
C-N
C-XC-OH
C=O
5-
a
bcd
e
C=OC=S
C=N-OH,C=N-HCC
CN
eC=O
fC=C
gC-CN
d
C-H
eC=C
fC-CN
e
C-OCH2OR
fC-OC（O）R
gC---OHC=O
e
C=O
fC=C
gC-C（O）Z
fC=C-OR;C=C-SRgC（OR）2;C（SR）2hC-OH
hC-CO2H
iC-CHO
h
iCO
h
CN
i
C-NH2;C-NO2
jC（O）X
jC=C
jC-Br
CCC=C
C-X
C-CH3
k
C-H
6-abc
d
RCCH
RCH2-SO2PhCC
C=C
7-
a
bc
CH-CXCH-CH
CX-CY
X
8-
a
bc
d
C-OHC-NH2C=O
C（O）Z
9-
a
C-X
eRCH（CO2H）-CH3
dCC
e
C-H
f-C（O）-CH3
g
OO
hXO
e
-C（O）-CH3
fC=O
gCC
hCCH
iCRR'=CHX
i
C=C
jC-OH
C-H
1-a
C-OH
eC=O
iC-CHO
bC-X
cC-NH2
dC-S
f
C=C
gC-CN
hC-CO2H
jC（O）X
1-a
C-OH
C-H
J.Org.Chem.2000,65,6179
ORCH2OS
OO
CH3
tosylate
toluenesulfonylchloride（s）
~$30/Kg
（1）.for1',2'alcohol:
O
CH3SCl
LiAlH
RCH2OSCH3
OO
mesylate
methanesulfonyychloride（l）~$30/Kg
i.p-TsCl//LiAlH4
RCH2OH
O
dryPy
4
RCH2-H
RCH2O
PhPh
SCF3
O
triflate
purificationtextbook
drypyridine:
fromCaH2anddistilled
ii.Ph2SiHCl/InCl3
PhPh
Ph2SiHCl/InCl3PhPh
CHCl2
via:
H
O
indiumtrichloride
OHrt,3hrHJOC,2001,66,7741.
Cl2In
Cl
SiPh2
InCl3
auniqueLewisacidcatalyst,acceleratedeoxgyenation
（2）.for3'alcohol:
i.ClC（S）OPh//n-Bu3SnH
CH3
CH3
OH
S
ClC
OPh
n-Bu3SnH
CH3
CH3
H
via:
S
OCOPh
SnBu3
S
OCOPh
CH3
CH3
thiocarbonate
ii.Et3SiH/Lewisacid
JOC,2000,65,6179.
（anester）
stericOK
C-X
C-H
Brn-Bu3SnH
H
in-Bu3SnH/AlBN
（1）.freeradicalreduction
AIBN
iiNaBH4/InCl3/CH3CN
Bu3SnH:
（l）,easytoremovePh3SnH:
（s）,hardtoremove
Me3SnH:
toovolatile,toxic
JACS,2002,124,906.
radicalreagent
（2）.hydridereduction
iLiAlH4
iiNaBH4
JACS,1972,94,8905.
JOC,1969,34,3923.
THL,1969,3095.
iiiNaBH3CN
NaBH3CN:
stableatpH5-6
hygroscopic,driedself,suggest:
buysmallamounteachtime
unstableinacid,formH2gas;stableinweakbase
ivLiBHEt3（superhydride）
JOC,1976,41,3064.
Br
H
（3）.metalreduction
i
ii
Na/NH3;Li/NH3;Na/EtOH
Zn;Fe;Sn;Mg
Mg/EtO
2
HO
2
（Grignardreagent）
Br
n-BuSnH
R
H
n-BuSnH
N
N
n-BuSn
R
R
CN
CN
-N2
CN
（AIBN）
n-BuSnBr
n-BuSn
azobisisobutyronitrileradicalinitiator
1-b
1-c
C-NH2
C-H
RCH2NH2
ArSO2Cl
RCH2NHSO2ArBuLi
RCH2NSO2Ar
（1）.
RCH2NH2
p-TsCl
BuLi
LiAlH4
RCH2-H
Hinsberg'stest
O
tosylamide
RCH2
-
BuH
N
SO2Ar
LiAlH4
RCH2-H
p-TsCl
NaHNaH
p-TsCl
CH3SCl
tosylimide
SO2Ar
（2）.
Ar-NH2Ar-H
NH2Cl
O
SO2Ar
weakerC-Nbond
（3）.（3）.
Ar-NH2
NaNO2
H3PO2
Ar-H
via:
Ar
N
NH2
NaH
ArNNH
ArNN
Ar-H
HCl
-ArSO2H
JOC,2001,66,8293.
（4）.
-
（4）.
RCH2NH2RCH2NMe3X
Ag2O
RCH2NMe3
OH-
R=CH2
R-CH3
1-d
C-S
C-H
radicalmechanism
EtO2C
JOC,1985,50,427.
EtO2C
RaneyNickel:
Ni-Alalloy,suspension
（1）.RaneyNi
（2）.Li/NH3
（3）.LiAlH4/CuCl2
NaBH4/NiCl2
HNMeO2C
JCSPerkinTransI,1973,654.
NCH2PhO
S
RaneyNi
HNMeO2C
NCH2Ph
H
burnfilterpaperifdrymechanismuncertain,probablyradical
NaBHEt3/FeCl2（orCoCl2,VCl3）
Chemistry:
R-SHR-S-RR2SOR2SO2R-SS-R
remove:
Hg+;Ni
1-e
C=OC-H
SH
HSS
Ra（Ni）
H
bestsuitableforarylketone（ArCOR）;notgoodforconjugateketone
O
BF3,
CH2Cl2SHH
preparation:
HgCl2intoZn
OHO
H
thioketal
（1）.Clemmensenreduction:
Zn-Hg/HCl
similar:
Sn/HClSH
acidic
C6H13
thioketal:
inerttoLAH;reactwithRaNi;smellterribleandstaylong;discardshoses
（2）.thioketal:
SH/BF3,CH2Cl2//RaNi
neutral
ONNH2
OH-
NNHH
OH-H
H
（3）.Wolff-Kishnerreduction:
N2H4,OH-,heat
basic
O
N2H4
NN
NNH
-N2
（4）.Pd-C/HCO
Pd-C
PhPh
majorside-product:
drawbackofthereaction
2NH4:
mild,efficientPhPh
HCO2NH4
（5）.Tosylhydrazonereduction（Shapiroreaction）:
Synthesis,2001,16,2370.
H
（modifiedWolff-Kishnerreduction）:
）
TsNHNH2//RED
NNTsH-
Hforacyclic,mayC=Csideproduct
O
（6）.enolderivatives:
Tf2O/N
//H2/PtO2
O
limit:
for-Hcompd.
REDchoice:
MeLi;NaBH3CN（good）BHO
LAH,NaBH4:
2groupcompeteatStanfordU.
B2H6:
veryflamable,fireifshootoutfromsyringe
（7）.Et3SiH/CF3COOH
NO2
Et3SiH
Ph
CF3COOH
NO2Ph
OO
H2
HOCF3SOS
CF3HH
JOC,1973,38,2675.
CCOO
N
OTf
CC
PtO2
CCH
PtO2+H2=Pt
1-f
C=CC-C-H
catalyst:
Pd-C
H2PtO2
H2,PtO2
RR
NTFA,60℃N
（1）.H2/cat
PtO2HO
Rh-C;Rh-Al2O3;OH
HOH
HOH
inaceticcondition
R=NHAc,NH2
（2）.HN=NH（diimide）
（3）.B2H6//RCO2H,heat
RhCl（PPh3）3
Ni
stereoselcetive:
samesideasOH（duetoHbond）
JOC,1993,58,4979.RhCl（PPh3）3
JOC,2002,67,7890.
CO2Me
ORhCl（PPh3）3O
ObenzeneO
CO2Me
（4）.n-Bu2SnI/MgBr2-Et2O//H3O+
OO
Wilkinson'scatalyst:
regioselective,preferisolateddoublebond
12hr
JACS,1979,101,7020.
H
via:
CH3CO2DH
solubleinorgsolvent,9Phgroup
$50/25g
BR
RD
prepareisotope
N2H2:
unstable;generatedinsitufrom"DEAD"（diethylazodicarboxylate）orfrom:
N2H4+H2O2;N2H4+Cu（II）+O2;NH2OH+NH2OSO3
JCS,PT1,1986,546.
EtO2C
NNCO2Et
OH-
HO2C
NNCO2H
RR
CCRR
HNNHR
OHHO
-2CO2
-N2
RCC
RR
OEt
O
n-Bu2SnIMgBr2-Et2O
H3O+OEt
O
via:
NN
OO
OEt
IO
IOEt
O
syn-additionHH
notradicalmech.
JOC,2001,66,8690.
Sn
HRR
HSn
RR
1-g
CCN
C-H
CN:
~X（pseudohalogen）,formKCN,NaCNwithIAelements
（1）.K/Al2O3
K/HMPA
JOC,1980,45,3227
notquitesame:
notforH-
RCCN
characteristcs:
IR,CMR
（2）.Na/NH3
whichis+?
HMPA:
hexamethylphosphoramide（Me2N）3P=O
=HMPT:
hexamethylphosphorictriamide（Me2N）3P=O
toxic?
b.p.~230C
highlytoxic,cancersuspectedagent?
yesforwhitemouse,uncertainforhuman
modifiedto:
NNO
1-h
CCO2HC-H
PhPh
RO
Hsolvent
（1）.particularstructure:
-CO2
O
PhN
PhPh
-CO2
NPh
（2）.normalstructure:
SOCl2//PhSeH//n-Bu3SnH
otherClsources:
PCl5;（COCl）2
oxalylchloride
ORCO2RH
RR
pyridiniumbetaine
（3）.organicelectrochemistry
CO2H
e-
O
SOCl2
OO
PhSeHn-Bu3SnH
CO2H
RCH2
COH
RCH2
CCl
RCH2C
SePh
RCH2H
（radicalmechanism?
）
organoseleniumchemistry
CHO
C-H
O
OH
（1）.RhCl（PPh3）3（Wilkinson'scat）
ClPPh3
Rh
PPh3PPh3
-PPh3
ClRh
PPh3
PPh3
RCH
RCPPh3
Rh
PPh3
（2）.Rh（DPPD）2+Cl-
oxidativeaddition
Cl
R
H
DPPD=Ph2P-CH2CH2-PPh2
Cl
Rh
rearrangement
O
C
PPh3
PPh3
Cl
R
reductiveelimination
H
+
Rh
C
PPh3
PPh3
O
C（O）X
-CH3
O
HSiEt3/B（C6F5）3
RCH3
R
Cl
JOC,2001,66,1672.
1-i
1-j
RC-OR
2-a
b
RC-OHRC-（OR）2
d
RC-H
eRC=C
cRC（O）OR
f
RC-CN
2-a
RC-OHRC-OR
application:
forprotectinggroup
generateH2,orbutanegas
trimethyloxoniumtetrafluoroborate
base:
NaH,n-BuLi,Ag2O
JOC,1988,53,2985.
JCS,1930,2166.
Megroup:
（1）.
-
Me:
base/CH3-XRC-OCH3
（2）.PhCH
CH3-X:
CH3I;CH3OSO2R;（CH3）3O+BF
PhCH2-Cl
4,（CH3）2SO4
i.
Williamsonethersynthesis,SN2type
ii.notagoodprotectinggroup,toostabletoconvertbacktoalcohol
Benzyl-group:
2-:
base/PhCH2-X
RC-OCH2Ph=RC-OBZl=RC-OBn
PhCH2-X:
PhCH2-Br:
reactivitygood
PhCH2-I:
reactivitybetterthanPhCH2Br,
i.abbreviation:
benzyl=PhCH2=Bzl=Bn
ii.deprotecting:
H2/Pd-C
（3）.allyl:
base/Br
RC-OCH2CH=CH2
（4）.t-Bu:
acidcat/RC-OtBu
acid:
H2SO4
H3PO4BF3-Et2O
generatedinsitu,PhCH2Br+NaI
CH3
t-Bgroup:
Williansonsynthesis（base,SN
2）notwork:
eliminationside-productwithbase
（5）.trityl:
py//Ph3C-BrRC-OCPh3=RC-OTr
Et3N/TMS-Cl
CH3SiCH3
Cl
CH3
Si
Cl
Tritylgroup:
（tirphenylmethyl）
i.SN1reaction
ii.abbreviation:
triphenylmethyl=trityl=-CPh3=-Tr
Brbase
（RO-Tr）
（6）.silyl:
Et3N/R3SiClRC-OSiR3
（7）.acetal/ketal:
（see3e）
N
/TBDMS-Cl
NH
TBDPS-Cl
NO2
F
NO2
CH3
Ph
SiCl
Ph
iii.
advantage:
highMW,easytohandle（smallamountbecomelargeamount）Silylgroup:
i.WilliansonsynthesisOK:
Si-Clbondlong
ii.stabilityofsilylinacid/base:
RC-O-TBDPS>RC-O-TBDMS>>RC-O-TBS
（8）.ArF/CsFROH
CsFRO
aromaticsubstitutionreaction
iii.
abbrev.:
TBDMS=tert-butyl-dimethylsilyl=TBS=
2-b
OR
RC-（OR）2RC-ORROR
O
RCH2OR
RCH2OCH2CH2OH
usuallycontainNO2,Fasleavinggroup
activator/hydridesourceR
O
（1）.h/HSiCl3
（2）.HCl/NaBH3（CN）
（3）.AlCl3/LiAlH4
OCH3
OCH3
OO
HCl
AlCl3
LiAlH4
OCH3H
OH
O
OCH3
2-c
O
RCOR
RC-OR
radicalmechanism:
SiCl3
t-BuO
RaNiwithC=S
O
（1）.
3
hv/HSiCl
OO
（2）.HCl/tBu-OO-tBu
JOC,1974,39,2470.
HCl
tBu-OO-tBu
（3）.Lawessonreagent/RaNi
（4）.BF
3/NaBH4
limitfor:
lactone
O
OLawessonreagent
S
ORaNiO
CH3O
SSOCH3
PP
SS
~PS
OAr
O
BF3
OAr
LawessonreagentJOC,1983,48,1127.
410
Ar
NaBH4
OOArO
2-d
RC-H
RC-OR
OH
I2/Pb（OAc）4
Oseemech-13
OIHOIHO
（1）.I2/Pb（OAc）4/hv
AngewChemIntEng.,1964,8,525.limit:
for5~6ringneighboringOHgroup
hv
e/Pt
NOR'MgBrNR'
（2）.OrganoelectroChemistry:
e-/Pt,R4NOTsNOH
Ph
R4NOTs
Ph
OH
（79%）Ph
（3）.NCS/MeOH
JOC,2002,67,4498.
HHHH
OCH3
limit:
forallylicalcohol
NNH2
O
NH
NCSN
O
MeOHN
H
NH2
2-eCC
C-C-OR
OC=C-OR
OHg（OC
CF）
OEtOH
peracid:
2-e.1CC
CC
C-C-OR
32H+gO
CCF3
NaBH4
OEt
CF3CO3H
CO3H
goodresult
i.Hg（OCOCF3）2,
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