Flashcards in Synthetic Transformations Deck (28)
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1)Hg(OAc)2, H2O , THF
2 ) NaBH4
Markov after of h and oh
1)Breaks c=c double bond forms
H2C-HgOAc on outer and adds oh to other
2) HgOAc comes off leaving CH3
Oxymercuration-demercuration
1
1) HG(OAc)2, HOR, THF
2) NaBH4
Markov add of h and or
1) c=c breaks HgOAc bonds to CH2
OR binds to ch
2) nabh4 breaks HgOAc off leaving CH3
Alkoxymercuration-demercuration
2
HBr, peroxide, heat/light
Antimarkov add of Br
C=C pi bond breaks
Br to less sub C
3
1)BH3, THF
2) H2O2, NaOH, water
Antimark add of cis oh&h trans to ch3
1) C=C pi bond breaks
Less substituted grabs bh2
2) bh2 comes off leaving oh
4
HX, cold, dark, no peroxide
(x=cl, Br, I)
Markov add of X
C=C pi bond breaks
X bonds to more sub C
5
Br2
Trans 2 Br's added
one then other
Alkene c=c pi breaks
6
MCPBA
Or
Perot acid
Added to alkene to form episode ring
Oxidation of Alkene
c=c pi bond breaks
C-C-O ring forms (epoxied ring)
7
1) strong base (nucleophile)
2) diluted acid (watery acid)
Epoxide ring opening (basic conditions)
Antimarkov OR w
1) Epoxide ring opens leaving O- on most sub C, OR adds to least sub C
2) h bonds to o- to give oh on most sub C (oh on most sub c)
8
H+ (H3O+)
HOR
Epoxied ring opening (acidic conditions)
Markov OR added
H added to epoxide ring tip
Epoxied ring opens to least sub C
OH on least sub C
OR bonds to most sub C
9
Br2, HOR
Markov addition of Br and OR to alkene
c=c pi bond breaks
Br bonds to least sub C
OR bonds to most sub C
10
CHCl3, KOH
Or
CH2I2, Zn(Cu)
Alkene Forms cyclopropane ring
C=C pi bond breaks
C-C-C ring forms
11
H2, Pt0 or Pd0
Syn add of h on bottom
C=c bond breaks
CH3 on Both C's move up
H's come up from bottom and bond to each C cis to each other
Catalytic hydrogenation
12
1) BH3, THF
2) H2O2, NaOH, H2O
Hydroboration oxidation
Antimark cis oh and h
trans to ch3
1) Alkene C=C bond breaks
OH bonds to least sub C after H bonds to most sub C
OH and H are cis to each other
13
H2/ Pt or Pd metal
Alkyne to Alkane
Breaks both pi bonds in cc triple bond
Replaced with H's
14
H2 / Ni2B
Or
H2/ lindlar catalyst
Alkyne to cis Alkene
Only breaks one pi bond of c
Leaves cis Alkene
15
Na0 (sodium metal)
NH3(l) (liquid ammonia)
Alkyne to Trans Alkene
Only breaks one pi bond of triple bond
Forms Trans Alkene
16
PCC
Oxidation of primary (1*) alcohol to aldehyde
Breaks h off C
Breaks h off the O forms double bond from C=O
Forms aldehyde
17
KMnO4
Or
Na2Cr2O7/acid/water
Or
CrO3/acid/water
Or
Pcc
Oxidation of secondary (2*) alcohol to ketone
Break h of C
Breaks h of O
c=o and c bonded to 2 R forms ketone
Or aldehyde into carboxylate acid adds O to H
Or 1* alcohol into carboxylic acid breaks of 2 H's from c and 1 from o
O=C bond forms and oh off c
Carboxylic acid
18
1) OsO4
2) H2O2 or NaHSO3
Syn add of two OH groups to pi bond
1)Pi bond breaks two sun o's attach to form Pental ring with Os at peak with 2 double bonds to 2 O's
2) ring breaks of leaving only cis os which form oh's
19
1) ozone O3
2) Zn, acetic acid
Ozonolysis
Turns to ketone and aldehyde
C=C bond cleaved with two O cap
Ex: c=o c=o
h stays h
20
1)KMnO4(hot)
Turns to ketone and carboxylic acid
Double bond cleaved caped with o's
Oxidized - lone H's become oh
Sometime breaks down
21
1)HX/ cold dark no peroxide (1 mole)
2) HX / cold dark no peroxide (excess)
1st HX Alkyne to Alkene with Markov add of X
2nd HX Alkene to alkane
Markov X added. twins
22
1) X2 ( 1 mol)
2) X2 (excess)
1) Alkyne to Alkene
Trans X's on each C
2) Alkene to alkane
Twin Trans X's on each C
4 total
23
D3O+
Or
Tautomerization
Vinyl alcohol or enol to ketone
C=C pi bod breaks and goes to oh
H breaks off o and goes to carbocation C+
24
H2O, H2SO4, HgSO4
Alkyne to ketone R-C(=O)C
Markov add of H2O to Alkyne
25
1) BH3, THF
2) H2O2, NaOH, H2O
Alkyne to R-C-C=O
Antimark add of h2o to alkyne
26
NaNH2 (Na+ and NH2)
Alkyne deprotonated
Alkyne C loses h and gets lone pair becomes C- stays Alkyne
Acetylide ion made
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