Alcohols:

- Alkenes
o Oxymercuration and demercuration: MORE substituted alcohol formed
o Hydroboration and oxidation: LESS substituted alcohol formed
The added H and OH are added syn
- Grignard
o Making reagent: alkyl halide and magnesium 0 (2Li/2Na/2K) with no water
o Reacts with aldehyde and ketone
o =O is replaced with replaced with O and R group on the Grignard reagent
o Reacts with esters
Requires 2 equivalent Grignard reagent
=O replaced with O and R group on the Grignard reagent
--OR replaced with R group on the Grignard reagent
o Reacts with epoxides
Has 2 reaction sites
-R group on the Grignard reagent adds to LESS substituted carbon (steric
hindrance), -OH forms from the =O on the more substituted (the other carbon)
o Grignard reagent will react with any proton source (super strong E
+
)

Reactions with Alcohols:
- Alcohol into alkyl halide R-OH to R-X
o Forward reaction
HX (acid with halide)
PX
3

SOCl
2

o Backwards reaction
Water in acidic or basic conditions
- Acid and base reaction with OH
o Metal with 0 oxidation state (Li/Na/K) acts as base and OH as acid
Makes alkoxide and hydrogen radical (hydrogen gas)
o Look at acids on both sides of reaction, the STRONGER acid LOWER pKa will drive the
reaction and win
o Realize PROTON TRANSFERS will happen first
o Relative acidity (basicity reversed)
ArOH > H
2
O > ROH > HCCH > NH
3
> RH
- Protecting groups
o TBDMSCl (a silyl chloride), temporarily REPLACES OH and can be reoxydized
o Deprotect using HF or TBAF (containing fluoride)

Ether:
- Alkyl halide with alkyl oxide; a substitution reaction and makes a ETHER (Williamson Synthesis)
o If alkyl halide is Ar-X or 3
o
(too steric for substitution); HINDERED OXIDE may result in
E1/2
LG is X
E
+
the R group in alkyl halide
N
-
the alkyl oxide
o To make the ALKYL OXIDE, we react alcohol with STRONG BASE NOT HYDROXIDE (NH
2
-
)

Epoxides:
- React a DB with a peracid (R--CO
3
H)
o R group can be Cl-Ar- or F
3
C-
o If you start E/Z you will make epoxide of the same orientation
o More substituted DB C=C
- React a DB with a NaOH and Cl
2
or HOCl and NaCl
o makes chlorohydrin (or whatever halide) intermediate
-OH group anti to Cl group
and then MORE NaOH (excess, specified)
again same orientation of epoxide forms
You can also start from the chlorohydrin

Reactions of epoxides and ethers:
- ETHERS do not react
- Epoxides react:
o In acidic conditions; diluted H
+
with alcohol better carbocation formed
The R-group forms on MORE substituted carbon
-OH is anti to R-group
Alcohol or SH, slight H
+

Dont use AMINES, or else the H
+
will protonate the amine
o In basic conditions; Na
+
with CH
3
O
-
(quench with acid) better orbital overlap
R-group forms on LESS substituted carbon
-OH is anti to R-group
C
-
or Grignard reagent
AMINES can be used (basic only)

Oxidation:
- PCC or PDC are MILD oxidizing agents (pyr. Weakens the chromate)
- Ag
2
O, KMnO
4
, and H
2
CrO
4
are HARSH oxidizing agents
- Primary alcohol
o MILD: makes aldehyde
o HARSH: Oxidizes alcohols AND carboxyl completely into CARBOXYLIC ACID (-CO
2
H)
- Secondary alcohol
o MILD/HARSH: makes a ketone (the other 2 C-C bonds must stay)
- Tertiary alcohol
o NO REACTION
- Ozonolysis = ozone (O
3
) with reducing agent
o Reducing agents include ZnHOAc, PPh
3
, Et
3
N, RSR
o Splits the C=C right in half and turns =C into =O to make ALDEHYDES and KETONES
o Ar groups will not react well (too stable)

Reduction
- NaBH
4
special selective for carbonyl groups (strong carboxylic acid)
- BH
3
works in hydroboration and works best for C=C; reduces carboxylic acid
- DIBAL/DIBALH and LiAlH(OR)
3
mild reducing agent
- H
2
with special catalyst for DB and TB
- Reactions
o Acid halide (carbonyl group)
Mild gives aldehyde
Harsh gives alcohol
o Esters
Mild gives aldehyde with alcohol (from the ether with R group)
Harsh gives alcohol with alcohol (from the ether with R group)
o Cyano-group (R-CN)
Mild gives aldehyde with amine
Harsh gives amide (carbonyl group attached to the carbon, NH
2
forms)
o Carboxylic acid (R-COOH) requires special reducing agent
BH
3
or LiAlH
4
to give alcohol =O turns into OH and H; the OH turns into H
o Amide
Mild gives aldehyde with amine
Harsh gives only amine
- NOTE: NaBH
4
gives selectivity to aldehyde over ketone (if in the same molecule and equivalency
only allows for one reaction)

Reactions of Aldehydes and Ketones (not including redox):
- Addition of alcohols
o Alde/ket with DRY H
+
with ROH (alcohol)
Hemiacetal intermediate formed with OH and OR
-OH replaced with OR so you get 2 OR
o Reverse, acetal with H
2
O with H
+

o Dilute protons
o Allows you to protect the carbonyl (because of reversibility)
- Addition of thiols (Wolff-Kishner)
o Alde/ket with DRY H
+
with RSH
Thiolhemiacetal intermediate
-OH is replaced with another SR
o Reversed with H
2
O with H
+

o SPECIAL: Ramey-nickel catalyst with H
2

Changes SR into H (C=O into C-H
2
)
Acidic conditions
- Addition of ammonia derivatives
o Primary amine (RNH
2
)
Replace the =O with =N-H
Makes an imine and water
To reverse use water and H
+

In semicarbazide, only the amine group reacts, AMIDES DONT REACT
o Secondary amine (HNRR)
Replace the =O with =N
+
-RR
You cannot break the C-C bond so positive charge left on N
Makes iminium ion and water
E2 reaction can occur, making best double bond (if there are possible hydrogens
to eliminate) enamine molecule
o Tertiary amine
NO REACTION
o Special case: hydrazine
H
2
N-NH
2
react with alde/ket and BASE (ex. NaOH)
You make C=O into C-H
2
like the Wolff-Kishner but in basic condition
Useful when extra H
+
can affect the product
- Wittig reaction
o Ylide formation, react Ph
3
P with X-CH
2
-R add base to pick off extra H
+

Ylene/ylide (C
-
formed)
Ph
3
P=O salts
o E if stabilized (trans); Z if non stable (cis)
o Stabilized if extra resonance other than ylene
Strong base non stable (NaH, BuLi, PhlLi, NaNH
2
)
Weak base stable (ie NaOH, KOH)
o In benzene rings
Electron withdrawing group in ortho/para STABLE
Electron donating group in any position UNSTABLE
No substituents mixture of E/Z (medium stability)