Synthetic Transformations

Question 0

1) HG(OAc)2, HOR, THF

2) NaBH4

Answer 0

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

Question 1

1)Hg(OAc)2, H2O , THF

2 ) NaBH4

Answer 1

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

Question 2

HBr, peroxide, heat/light

Answer 2

Antimarkov add of Br
C=C pi bond breaks
Br to less sub C

Question 3

1) BH3, THF

2) H2O2, NaOH, water

Answer 3

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

Question 4

HX, cold, dark, no peroxide

x=cl, Br, I

Answer 4

Markov add of X

C=C pi bond breaks
X bonds to more sub C

Question 5

Br2

Answer 5

Trans 2 Br’s added
one then other

Alkene c=c pi breaks

Question 6

MCPBA
Or
Perot acid

Answer 6

Added to alkene to form episode ring
Oxidation of Alkene

c=c pi bond breaks
C-C-O ring forms (epoxied ring)

Question 7

1) strong base (nucleophile)

2) diluted acid (watery acid)

Answer 7

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)

Question 8

H+ (H3O+)

HOR

Answer 8

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

Question 9

Br2, HOR

Answer 9

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

Question 10

CHCl3, KOH
Or
CH2I2, Zn(Cu)

Answer 10

Alkene Forms cyclopropane ring

C=C pi bond breaks
C-C-C ring forms

Question 11

H2, Pt0 or Pd0

Answer 11

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

Question 12

1) BH3, THF

2) H2O2, NaOH, H2O

Answer 12

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

Question 13

H2/ Pt or Pd metal

Answer 13

Alkyne to Alkane
Breaks both pi bonds in cc triple bond
Replaced with H’s

Question 14

H2 / Ni2B

Or

H2/ lindlar catalyst

Answer 14

Alkyne to cis Alkene

Only breaks one pi bond of c
Leaves cis Alkene

Question 15

Na0 (sodium metal)

NH3(l) (liquid ammonia)

Answer 15

Alkyne to Trans Alkene

Only breaks one pi bond of triple bond
Forms Trans Alkene

Question 16

PCC

Answer 16

Oxidation of primary (1*) alcohol to aldehyde

Breaks h off C
Breaks h off the O forms double bond from C=O
Forms aldehyde

Question 17

KMnO4 
Or 
Na2Cr2O7/acid/water
Or
CrO3/acid/water
Or
Pcc

Answer 17

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

Question 18

1) OsO4

2) H2O2 or NaHSO3

Answer 18

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

Question 19

1) ozone O3

2) Zn, acetic acid

Answer 19

Ozonolysis
Turns to ketone and aldehyde

C=C bond cleaved with two O cap
Ex: c=o c=o
h stays h

Question 20

1)KMnO4(hot)

Answer 20

Turns to ketone and carboxylic acid

Double bond cleaved caped with o’s
Oxidized - lone H’s become oh

Sometime breaks down

Question 21

1) HX/ cold dark no peroxide (1 mole)

2) HX / cold dark no peroxide (excess)

Answer 21

1st HX Alkyne to Alkene with Markov add of X
2nd HX Alkene to alkane
Markov X added. twins

Question 22

1) X2 ( 1 mol)

2) X2 (excess)

Answer 22

1) Alkyne to Alkene 
Trans X's on each C
2) Alkene to alkane 
Twin Trans X's on each C 
4 total

Question 23

D3O+
Or
Tautomerization

Answer 23

Vinyl alcohol or enol to ketone
C=C pi bod breaks and goes to oh
H breaks off o and goes to carbocation C+

Question 24

H2O, H2SO4, HgSO4

Answer 24

Alkyne to ketone R-C(=O)C

Markov add of H2O to Alkyne

Question 25

1) BH3, THF

2) H2O2, NaOH, H2O

Answer 25

Alkyne to R-C-C=O

Antimark add of h2o to alkyne

Question 26

NaNH2 (Na+ and NH2)

Answer 26

Alkyne deprotonated
Alkyne C loses h and gets lone pair becomes C- stays Alkyne
Acetylide ion made

Question 27

1)H2O, H2SO4

Answer 27

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