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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

27

1)H2O, H2SO4

R-CN( triple bond)
N gains an H
C=O
Eventually becomes carboxylic acid
Nitrile hydrolysis