1

Chapter 11
Alcohols, Ethers and Phenols
Alcoholsstructure, nomenclature and properties as before
Phenolbenzene with OH attached
OH

EtherROR, where R = alkyl group

O

Simple ethers are named using the alkyl group attachements. Butyl pentyl ether above.
ethyl methyl ether
O

tert-butyl ethyl ether

diethyl ether
O

In more complex molecules, ethers are named as alkyloxy. Examples methoxy, ethoxy

OH

6-tert-butoxy-5-ethoxy-2-methoxy-4- methyl-3-octen-1-ol

Cyclic ethers3-sidedoxirane, 4-sidedoxetane, 5-sidedTHF, 6-sided1,4-dioxane

O

Physical properties of ether

No hydrogen bonding possible so ethers have low boiling points similar to hydrocarbons
However because of Oxygen ethers are good solvents can dissolve organics and ionics.
Some common examplesMethanolwood alcohol, originally prepared by distillation of wood
toxic, small quantities can cause blindness, large quantitiesdeath
Ethanoldrinking alcohol, made through fermentation of sugars
sugars can come from many sources mostly grain, hence, grain alcohol
Fermentation can only generate maximum 12-15%v/v of ethanol due to high
solubility of water. To get higher percentages water must be distilled away.
Hence Jack Daniels DistillariesProof = 2 xs the %. 100 proof = 50%.
Even with distillation highest percentage possible is 95%. The last 5% of
water can not be eliminated because it forms an azeotrope that boils at lower
temperature than the ethanol itself. This is pure grain alcohol190 proof =
95%. To remove the last 5% water impurity, benzene is added and a new
azeotrope forms that boils even lower than the water/ethanol azeotrope. 200
proof = 100 % is called absolute alcohol. It is denatured by adding a toxic
substance such as methanol or benzene. This is called denatured alcohol.
Ethylene glycolantifreeze
Diethyl etherflammable used as anesthetic

Cl
F3C

CH3OH CH3CH2OH
Methanol Ethanol

OH

OH

HFClC

CF2H

CF2H

Ethylene glycol

Isofluorane

Enfluorane

Synthesis of alcohols from alkenes

1) Acid-catalyzed hydration of alkenesChapter 8, not useful synthetically.
Rearrangements make this a very non useful reaction. Markovnikov addition.
OH

H3O

2) Oxymercuration-DemercurationMarkovnikov addition. Usually less than one

hour in 90-100% yields.
1) H 2O/Hg(acetate)2

OH

THF
2) NaBH 4/OH

Hg+OAc + OAc-

Hg(OAc)2
H2O

H2O

Like the halohydrin intermediate

OH2

Hg
OAc

The mechanism for the removal of the HgOAc is not understood.

HgOAc

3) Hydroboration-OxidationAnti-Markovnikov addition
1) BH3:THF
3
2) H2O2/OH
H

H
B

OH

Boron adds to less substituted side.

Hydrolyze

R=
B(OR)3

Transition state.

Repeat twice
syn addition

Transition state collapses.

H

BH2

Repeat twice

O
B

H
H

Reaction of Alcohols
The OH of the alcohol is basic and can act as a nucleophile. It is a very bad leaving
group. Protonation of the alcohol makes the OH a good leaving group. Water has a pKa
of 15.7. Most alcohols have higher pKa than water(the exception being methanol). This
is due to the steric hindrance created by the alkyl groups. The large the alkyl group =
higher the pKa which = less acidic.
Acidity
Water > ROH > Alkyne > H2 > NH3 > RH
Basicity
R- > NH2 - > H- > Alkynide- > RO - > OHCONVERTING OH TO GOOD LEAVING GROUP
Mesylates, Tosylates and Triflates make very good leaving groups. Ms-Cl, Ts-Cl,
Tf-Cl in the presence of base converts alcohols to those very good leaving groups.
These mesylates, tosylates and triflates can undergo SN2 reactions very easily. In
the process of converting OH to these good leaving groups the stereochemistry of
the carbon remains unchanged(retention of configuration). However once the SN2
reaction occurs, then inversion of configuration occurs. Triflates are such good
leaving groups that even vinylic cations can form.
O Ms

Base(N aH ...)/MsCl
OH

O
Cl

O Ts

Base(NaH ...)/TsCl

Base(N aH...)/TfCl

Ms = R = CH3
OT f

Ts =

CH 3

Tf = R = CF 3

OH

B
Cl

OL

OL

L = Ms, Ts or Tf

To prepare Ms, Ts or Tf add PCl5 to the corresponding alcohol.

O

PCl5
HO

Ms = R = CH3

Cl

Ts =

CH3

Tf = R = CF3

CONVERTING ALCOHOLS TO ALKYL HALIDES

Acids such as HCl and HBr can be used to convert alcohols to alkyl halides.
These reactions lead to carbocations and rearrangements(Primary and methyl still
use SN2 mechanism to form the alkyl halides). HCl and HBr will usually produce
alkylhalides instead of elimination(dehydration) products because Cl and Br are
good nucleophiles. Recall if you want dehydration you add sulfuric acid or
phosphoric acid. HCl and HBr work fine for allylic, benzylic and tertiary
alcohols. However primary and secondary are too unreactive to work with HCl.
So lewis acids are usually added to increase the reactivity.
Phosphorous tribromide and thionyl chloride are modern alternatives that work
extremely well. With primary and secondary alcohols phosphorous tribromide
and thionyl chloride proceed with no carbocations and no rearrangements.

Br

OH

PBr 3

PBr2
O

HOPBr2

This can react twice more with alcohol to

brominate the alcohol

Br

O
Cl

OH

Cl

Cl

Cl

Cl

Cl

Cl-

trialkyl amines(such as triethylamine(TEA))

are used to scavenge the HCl that is formed
in this reaction.

Synthesis of Ethers
BY DEHYDRATION OF ALCOHOLS
Primary alcohols in the presence of acids create ethers with the elimination of
water. Secondary and tertiary do not work well. Alkenes form
instead(dehydration). Also mixed ethers do not form using this method.
2
OH

H2SO4
O
o

Reactions works ok with 1 since they are hard to dehydrate.

OH

H2SO4

H2SO4

OH

2 and 3 alcohols are easily dehydrated

OH

H2SO4
O

+
OH

Does not form.

WILLIAMSON SYNTHESIS
The alcohol is deprotonated with a base such as sodium hydride. Then it reacts in
an SN2 fasion with an alkyl halide. This results in the formation of an ether.
Problem 11.20retention vs. inversion. One reaction only occurs at the oxygen.
Therefore, retention of configuration of the original carbon is observed. The other
reaction involves an SN2 attack and inversion of configuration.
1) NaOCH3 2) CH3I
OH

OH

1) NaOEt 2) CH3CH2OTs

OK

1)

OMs

2)

OH

The alcohol can be 1 , 2 , or 3 . The

base should be an alkoxide base such as
sodium ethoxide. The leaving group can be
halogen or sulfonate. This is SN2 reaction.
o

Therefore, 1 or 2 carbon attached to leaving

group only.

10

PROTECTING GROUPS
Ethers can be used to protect alcohols. The alcohol is converted into an ether that
is unreactive. Then reactions can be carried out on the compound without
affecting the alcohol. Later the ether is removed to reveal the unchanged alcohol.
The protecting group should be fairly nonreactive and should be easily removable.
Tert-butyl ether is an OK protecting group. It is removed by dilute acid. One of
the more modern preferred protecting groups is tert-butyldimethylsily
ether(TBDMS) which is a large bulky group that is nonreactive to most reagents.
It is easily removed in the presence of fluoride ion(TBAFtetrabutylammonium fluoride).
OH

O TBDMS

TBDMS-Cl
im idazole/DMF
(pyridine can also be used)

T BDMS-Cl =
Si

OR

OP

P = protecting
group

Bulky group. Can withstand pH from 4-12.

Cl

OH

OTBDMS

TBAF/THF

TBAF =

OR (B u) 4NF

Silicon-fluorine is one of the strongest covalent bonds.

Fluorine seeks out the silicon and bonds to it.

11

REACTIONS OF ETHERS
Ethers in general have low reactivity and usually act as solvents which can
dissolve both covalents and ionics. The oxygen of the ether is basic and
nucleophilic so some reactions are possible. Ethers react with strong acids to
form alkyl halides.
Br
O

HBr

AND
Br

EPOXIDES
Epoxides are a special class of ethers. Epoxides are three-membered cyclic
ethers. Alkenes will in the presence of peroxy acids(such as MMPP) will convert
into epoxide. In the formation of the epoxide the stereochemistry of the double
bond is retained(lik e in the Diels-Alder reaction). Epoxides are extremely
reactive. Dilute acids can open up the epoxide to form a diol. Epoxides can also
undergo nucleophilic attack.

Just like in the halohydrin reaction from chapter 8,

the nucleophile attacks the more substituted carbon of the epoxide if the reaction
is acid-catalyzed(formation of carbocation-like intermediate). If the reaction is
base-catalyzed the nucleophile attacks the least substituted carbon(SN2 reaction).
The attack of the nucleophile on the epoxide leads to an anti-product. If you use
an alkoxide base(methoxide) the reaction produces a reactive intermediate. This
reaction keeps repeating creating a polymer chain. This is called anionic
polymerization. Methanol can be added to quench(stop) the reaction.

12

M M PP

O
O

OOH

M M PP =

OH

OH
O

H+

+
HO

HO

This is similar to the addition of acids to non-cyclic ethers. This is an

anti-hydroxylation of an alkene. Unlike KMnO4 and OsdiO4 which give syn
dihydroxylations. This reaction is analagous to the bromination reactions of Ch. 8.
Acid-catalyzed reactions can be carried out with other nucleophile. This will also
lead to anti-addition. The incoming nucleophile adds to the more substituted carbon,
as in the halohydrin reaction. The intermediate is unsymmetric and resembles a carbocation.
Cl
O

HCl

HO

Bases(nucleophiles) can also be used to open cyclic ethers(they can not open non-cyclic
ethers). The base-catalyzed reaction is a SN2 reaction. This also leads to anti-addition.
The incoming nucleophile attacks at the least substituted carbon.
OH
O

NaCl

Cl

Stronger nucleophiles are needed. I used

Cl just to make the point.

13

CROWN ETHERS
Polar aprotic solvents greatly enhance and speed up SN2 reactions. However, there
are disadvantages to polar aprotic solvents. They usually have high boiling points
making them tough to remove at the end of the reaction. They need to be purified
to be used in reactions(distilled). This is costly and time-consuming. Also at high
temperatures, polar aprotic solvents can decompose. Nonpolar aprotics would be
excellent solvents. Nonpolar aprotics would still greatly enhance SN2 reactions
but without all the problems of polar aprotics. Benzene, toluene, hexanes,
dichloromethane are examples of nonpolar aprotics. They are all low boiling
point and fairly easily purified. The problem is the nonpolar aprotics do not
dissolve ionic reagents because of their nonpolar nature. SN2 reactions usually
require ionic reagents(sodium iodide, potassium bromide). A recent
development called phase-transfer catalysts(PTC) help solve this problem. PTC
are both hydrophilic and lipophilic. They can go into the aqueous layer grab the
anion and then bring it into the organic layer where the reaction will take place.
They will then bring the leaving group back to the aqueous layer and pick up
another anion to start the process over again. Tetrabutylammonium fluoride is an
example of a PTC. SN2 reactions work extremely well with PTC. Other reactions
are possible. Oxidation with potassium permanganate can be carried out with
PTC. A test for alkenes is to take a potassium permanganate solution with TBAF.
An unknown is added to the permanganate(purple) solution. If the unknown
contains double or triple bond then the purple solution will turn brown.

14

Crown ethers are also good PTC. Crown ethers can completely solvate the cation
of the ionic substance creating a naked anion which then undergoes an SN2
reaction. The crown ether acts as the host and the cation that is trapped is called
the guest. Crown ethers are named x-crown-y. X stands for the total number of
atoms. Y is the number of oxygens. 18-crown-6 is especially good at solvating
potassium.

O
O

36-crown-12

15

REACTIONS FROM CHAPTERS 8, 11 and 12

HCl

Cl

HBr/CCl4

Br
Br

HBr/H2O2

Br

Br2/H2O

OH

Br

Br2

Br

H3O+

OH

1) HgAcetate, THF, H2O

2) NaBH4, NaOH
OH

OH

1) BH3:THF
2) H2O2, OH-

1) Hg(O2CCF3), CH3CH2CH2OH
2) NaBH4, NaOH
OCH2CH2CH3

16

Diazomethane

CH2I2/Zn(Cu)/diethyl ether

MMPP
O

1) MMPP

OH

2) H

OH
-

KMnO4, OH , H2O, cold

OH
OH

1) OsO4, pyridine
2) NaHSO3, H2O
OH
OH
Br

Br2, H2O

1) MMPP
2) HBr

OH

Br

1) MMPP
2) NaBr

OH

OH

Br

17

1) KMnO4, OH-, H2O

heat
5

2) H3O

3
4

1
2

OH

a
b

OH

1) KMnO4, OH-, H2O

heat
5

2) H3O+
7

OH

1) KMnO4, OH-, H2O

heat
2) H3O+

7
6
7

4
5

2
3

O
a

OH

1) KMnO4, OH-, H2O

heat

6
7

4
5

2
3

2) H3O

O
+
6
7

O
b
c

18

1) O3, CH2Cl2, -78oC

2) Zn, AcOH
5

3
4

1
2

a
b

H
O

1) O3, CH2Cl2, -78oC

5

2) Zn, AcOH
7

O
a
H

H
O

1) O3, CH2Cl2, -78oC

2) Zn, AcOH

7
6
7

4
5

2
3

O
a

6
7

4
5

1) O3, CH2Cl2, -78oC

c

2
3

2) Zn, AcOH

6
7

O
b
c

19

Br

1 mole HBr
Br

Br

2 moles HBr
Br

1 mole Br2
Br

Br

Br

2 moles Br2

HgSO4, H2SO4, H2O

Br

Br

1) O3
O

2) Zn, AcOH
or

1) KMnO4, OH5

2) H

1) O3

a
H

2) Zn, AcOH

OH

OH
O

or
-

1) KMnO4, OH
4

2) H

OH

O
a

1) O3

OH

2) Zn, AcOH
or

1) KMnO4, OHa

2
3

2) H+

c
d

1
2

c
d

OH
O
a

OH

20

OH

OTs

NaH, TsCl

OH

OTf

NaH, TfCl

OH

OMs

NaH, MsCl

OH

OTBDMS

TBDMS-Cl, pyridine
OH

OH

1) TBDMS-Cl, imidazole
2) TBAF/THF

OH

Br

HBr

OH
Br

PBr3

OH

OH

Br

PBr3

OH

Br

OH

SOCl2

Cl

Br

21

OH

H2SO4
5
6

OH

4
3

H2SO4
5

OH

H2SO4

NO REACTION
ONLY PRIMARY WORKS

H2SO4

NO REACTION
ONLY PRIMARY WORKS

OH

1) NaOMe
2) pentyl bromide

OH
5

2
3

1) NaOEt
2) hexyl iodide

OH

OH

1) NaH Br
2)

22

OH

H2CrO4
O

OH

OH

KMnO4, OH-, H2O, Heat

OH
O

OH

PCC
H
O

OH

Jones
OH

H2CrO4
OR
KMnO4, OH-, H2O, Heat

OH

H2CrO4
OR
KMnO4, OH-, H2O, Heat

NO REACTION
TERTIARY ALCOHOLS
DO NOT OXIDIZE

1) NaBH4 or H2/Pd or Na/MeOH

or LAH
2) H3O

1) NaBH4 or H2/Pd or Na/MeOH

OH

or LAH

OH

2) H3O+
H
OH

OH

1) LAH
2) H3O+
OH

OCH3

1) LAH
2) H3O+

23

OH

O
MgBr

1)
H3O+

2)

OH

MgBr

1)
H3O+

2)

O
MgBr

1)

H3O+

2)

OH

OH

MgBr

1)
H3O+

2)

OR

MgBr

1)
O

H3O+

2)

OH

Grignard's attack less-substituted carbon

OH

1)
H 3O +

2)

OH

1)
H 3O +

2)

1)
O

H3O +

2)

OH

1)
H 3O +

2)

OR

1)
O

2)

H 3O +

Alkynide's attack less-substituted carbon

OH

24

Br
f

1) 2 Li/ether
2) CuI
3) heptyl bromide

b
c

4
5

f
g

2
3

d
e

b
c

Br

1) 2 Li/ether
2) CuI
3) phenylbromide

b
c

Br

1) 2 Li/ether
2) CuI
3) Br
1

HOW DO YOU MAKE THIS?

d
b

1) 2 Li/ether
2) CuI
3) Br

a
Br

4
3

6
5

25

HOW DO YOU MAKE THIS?

d
b

b
Br

1) 2 Li/ether
2) CuI
3)
Br

Br

1) 2 Li/ether
2) CuI
3)
Br

d
Br

1) 2 Li/ether
2) CuI
3) Br

26

Bromination

Br

BrBr

Br

Br
Br

BrBr
Br

Conversion to a good leaving group

OH

B
Cl

OL

OL

L = Ms, Ts or Tf

27

Converstion of alcohol to halide

Br

OH

PBr3

PBr2
O

HOPBr2

This can react twice more with alcohol to

brominate the alcohol

BrO
Cl

OH

Cl

Cl

Cl-

O
H

O
Cl

Cl

Cl-

trialkyl amines(such as triethylamine(TEA))

are used to scavenge the HCl that is formed
in this reaction.

28

Oxymercuration

1) HgAcetate/THF/H2O
2) NaOH/NaBH4
OH
O

HgAcetate = Hg(OCCH3)2

OCCH3 = Ac

other steps

MECHANISM
O

HgOAc + OAc

Hg(OAc)2

HgOAc

H
O

O
O

!+
HgOAc

!+

HgOAc

29

Hydroboration
OH

1) BH3:THF

H
-

2) H2O2/OH

MECHANISM
+ enatiomer

H
H

B
H

B
H

unstable
intermediate

B
B

OH

3
R
OR

R
B
R

OR

repeat 2x's

RO

OR
B

OR

RO

OR

RO

RO

OH

OH

O
R

OH
H

ROH

30

Reduction of ketone/aldehyde
OH

1) NaBH4
R(H) 2) H 3O +
H3 B

R(H)

H
H

OH2

R(H)

Oxidation of alcohol
[Cr]
R(H)

R(H)

OH
O
H

Cr

O
H

H 2O
H

R(H)

R(H)
O
O

H 2O

HO
HO

O
Cr

O
HO

Cr

O
H

O
H

R(H)

O
HO
H2 O

O
Cr
O

31

OH

BH3

H+
BH2

OH
O-

OHR 2B

O
OH

BR2

32

Chapter 11 Homework

Name:

1. For the reactions on the next two pages, indicate if they are Markovnikov or anti-Markovnikov, syn or
anti addition. Also indicate which reactions are regioselective and which are stereospecific.

HCl

Cl

HBr/CCl4

Br
Br

HBr/H2O2

Br

Br2/H2O

OH

Br

Br2

Br

H3O+

OH

1) HgAcetate, THF, H2O

2) NaBH4, NaOH
OH

OH

1) BH3:THF
2) H2O2, OH-

1) Hg(O2CCF3), CH3CH2CH2OH
2) NaBH4, NaOH
OCH2CH2CH3

33

Diazomethane

CH2I2/Zn(Cu)/diethyl ether

MMPP
O

1) MMPP

OH

2) H

OH
-

KMnO4, OH , H2O, cold

OH
OH

1) OsO4, pyridine
2) NaHSO3, H2O
OH
OH
Br

Br2, H2O

1) MMPP
2) HBr

OH

Br

1) MMPP
2) NaBr

OH

OH

Br

34

2. Fill in the products for the following reactions.

Excess HCl
PBr5

SOCl2

1) NaH/Tf-Cl
2) NaSH

OH

MMPP

1) MMPP
2) Excess HCl
1) TBDMS-Cl
2) BH3:THF
3) H2O2/OH4) NaH/CH3I
5) TBAF
6) NaH/TsCl
7) NaOMe/MeOH

1) MMPP
2) TBDMS-Cl
3) NaSH
4) PBr5
5) TBAF

35

3. Fill in the reagents needed to accomplish these changes.

Br

Br

OH

Br

Br

Br

Br

O
O
OH

OCH3
Br

OH

Br
OH

H3CO

36

KEY
For the reactions on the next two pages, indicate if they are Markovnikov or anti-Markovnikov, syn or anti
addition. Also indicate which reactions are regioselective and which are stereospecific.

HCl

Markovnikov and Regioselective

Markovnikov and Regioselective

Cl

HBr/CCl4

Br
Br

HBr/H2O2

Anti-Markovnikov and Regioselective

Br

Mark., Regio, Anti Addition, Stereo.

Br2/H2O

OH

Br2

Br

Anti-Addiction, Stereo.

Br

H3O+

Markovnikov and Regioselective

OH

1) HgAcetate, THF, H2O

2) NaBH4, NaOH

Markovnikov and Regioselective

OH

1) BH3:THF

OH

Anti-Mark., Regio, SYN Addition, Stereo.

2) H2O2, OHMarkovnikov and Regioselective

1) Hg(O2CCF3), CH3CH2CH2OH
2) NaBH4, NaOH
OCH2CH2CH3

37

Diazomethane

Syn addition, stereospecific

Syn addition, stereospecific

CH2I2/Zn(Cu)/diethyl ether

Syn addition, stereospecific

MMPP

1) MMPP
2) H+

OH

Anti-addition, stereospecific

OH
-

KMnO4, OH , H2O, cold

Syn addition, stereospecific

OH
OH

1) OsO4, pyridine
2) NaHSO3, H2O

Syn addition, stereospecific

OH
OH

Br2, H2O

1) MMPP
2) HBr

Mark., Regio, Anti, Stereo.

Anti-Mark., Regio, Anti, Stereo.

Mark., Regio, Anti, Stereo.

OH

Br

1) MMPP
2) NaBr

OH

Br

OH

Br

38

2. Fill in the products for the following reactions.

Cl

Cl

Br

Excess HCl
SOCl2

PBr5

Cl

1) NaH/Tf-Cl
2) NaSH
MMPP

OH

SH

1) MMPP
2) Excess HCl
1) TBDMS-Cl
2) BH3:THF
3) H2O2/OH4) NaH/CH3I

1) MMPP
2) TBDMS-Cl
3) NaSH
4) PBr5
5) TBAF

OH

Cl

5) TBAF
6) NaH/TsCl
7) NaOMe/MeOH

Cl

Br

OCH3
OH

SH

OH

39

3. Fill in the reagents needed to accomplish these changes.

Br

Br

HBr

1) NaH, TfCl
2) NaBr

OH

1)

Br

Br

1) NaOCH3
2) Ethyl iodide

OK

Br

2) MMPP
Br

O
O
OH

1) TBDMS-Cl
2) NaBr
3) NaH, CH3I
4) TBAF

1) TBDMS-Cl
2) HBr
3) NaH, CH3I
4) TBAF
OCH3
Br

OH

Br
OH

H3CO

40

Homework

Name:

1. Fill in the products of these reactions.

1) MMPP
2) H+

1) MMPP
2) HBr

1) MMPP
2) NaSH
1) Hg(O2CCF3),
Propanol
2) NaBH4, NaOH

PBr3

HBr
TBDMS-Cl/NaH

OH

SOCl2

41

2. For the following, fill in the reagents.

OH

OH

OH
OH

OH

OH

HO

OCH3

42

3. Show the mechanisms for the following.

HBr/H2O2

Br

Br

OH

PBr3

43

Cl

OH

SOCl2

OH

1) HgAcetate/THF/H2O
2) NaOH/NaBH4

44

1) BH3:THF
2) NaOH/H2O2
OH

45

Homework KEY
1. Fill in the products of these reactions.
OH
OH
OH
Br

1) MMPP
2) H+

1) MMPP
2) HBr
SH

1) MMPP
2) NaSH

OH

1) Hg(O2CCF3),
Propanol
2) NaBH4, NaOH
OCH2CH2CH3

Br

PBr3

Br

HBr
TBDMS-Cl/NaH
OTBDMS

SOCl2

Cl

46

2. For the following, fill in the reagents.

OH

1) BH3:THF
2) H2O2, OH-

OH

1) NaH
2) Cl

OH
OH

KMnO4, H2O, cold

OH

1) TBDMS-Cl
2) BH3:THF
3) H2O2, OH4) NaH 5) CH3I
6) TBAF 7) TfCl
8) NaH 9) MMPP 10)H+

OH

HO

OCH3

47

5. Show the mechanisms for the following.

HBr/H2O2

Br

Heat or h

2 RO

ROH + Br
H

Br

Br

Br
Br

Br

PBr3

PBr2
O

Br-

Br

Br

OH

48

Cl

OH

Cl

Cl

O
H

S
O

Cl

Cl-

1) HgAcetate/THF/H2O
2) NaOH/NaBH4
HgOAc

other steps

OH
O

HgOAc

H
O

H
O

H
HgOAc

HgOAc

49

1) BH3:THF
H
H

2) NaOH/H2O2

B
OH

H
H
H

OBR2
H

O
RO

OR

BR2
O

O
OH

BOR2

OH