Web of Reactions

H O NaH Br Br Br

u TH (CN F )L i 2,

O H + OH O H H

O OH + O
2O

HO C's added

M e

2C

OH

2,

H2O, H3O+

e.g. HO

OH

O3 S 1) Me 2 2)

1) H 2) g(O an NaB Ac) 2 ti ad H4 , , EtO di tio OH H n

Br2 addi tion HF 1) BH 3, T OH HO 2) H 2O 2, w/ O anti-Markovnikov, yn addition s , H2 n less substituted retentio Ac) 2 OH ROH (O H 4, on Hg ti 1) ) NaB ddi 2 ti a OH an

, n Br 2 O io H 2 dit ad ti an

1) O 2) 3 H 2O

anti

BA on CP diti m d a n sy

trans glycol O + H H H O

e.g.

OH

H5IO6

OsO4, then H2O HO syn addition cis glycol H2 , Pd/C CH syn additio n 2I sy 2 , Zn /C na u dd itio n

x ero r, p HB HBr

OEt

anti-Markovnikov, less substituted R-Br peroxide reagents, except for H2O2, may be used carbocations = hydride shift, alkyl shift, ring expansion possible OH Br Br

attack at less substituted C

basic conditions or organometallic reagents

e.g. Me2Cu(CN)Li2 Cl

H2SO4, H2O
1

s ide
acidic conditions 3

attack at more substituted C

e.g. H2O, H3O+ OTs

SOCl2 best with 1 ROHs

S py OCl rid 2 , ine

PBr pyrid 3 , ine

, Cl e Ts idin r py

PBr3 best with 1 ROHs

Br

OH
4

MsCl, pyridine
T py f2 O rid , ine

OMs

PO 3

HB r, O

OTf

H Na eI 1) ) M 2

PCC, CH 2Cl 2

2S

Br 2 ROH most likely via SN1, so stereochem lost due to (+) O

OMe

Alkylating agents other than MeI: Me Me Me Me O S BF NO3 Me 4 Me

K2Cr2O7 in aqueous H2SO4 may also be used