Organic Chemistry I Synthesis Definitions - Dr. Straumanis

1. Hg(OAc)2, H2O/THF
2. NaBH4

-Oxymercuration/demarcation
-converts alkene to alcohol (breaks double bond + adds H and OH)
-Markov regio
-Anti stereo

1) Hg(OAc)2, HOR, THF
2) NaBH4

-Oxymercuration/demarcation
-breaks double bond + adds H and OR
-Markov regio
-Anti stereo

1) BH3, THF
2) H2O2, NaOH

- breaks double bond
- anti-Markovnikov addition of OH

1) HBr
2) ROOR' (peroxide)

- breaks double
- anti-Markovnikov addition of Br

1) Br2

- trans addition only
- breaks double bond
- forms epoxide ring before adding second Br

1) MCPBA

- breaks double bond
- alkene -> epoxide

1) strong base 2) dilute acid

- breaks epoxide ring and adds O- and OR (trans)
- dilute acid: replaces O- with OH

1) H3O+, HOR 2) Br2, HOR

- breaks the double bond
- Adds OR and Br in a trans way

1) CHCl3, KOH

- breaks the double bond
- adds CCl2 cyclopropane ring

1) CH2I2, Zn(Cu)

- breaks the double bond
- adds CH2 cyclopropane ring

1) BH3, THF
2) H2O2, NaOH, H2O

- breaks double bond
- anti-Markovnikov addition of OH

Catalytic Hydrogenation: H2, Pd metal or Pt medal

reducing an alkene by adding molecular hydrogen to double bond with aid of metal catalyst. e.g. pt, pd, ni. takes place on surface of metal so it does syn addition

1) H2/ Pt or Pd metal

ALKYNE:
- reduces double bond to single completely

1) H2/ Ni2B/Lindlar catalyst

ALKYNE:
- reduces triple bond to double bond
- syn. transformation

1) Na metal, NH3 (l)

ALKYNE:
- reduces triple bond to double bond
- anti. transformation

1) PCC

- turns OH to O with double bond
- 1-degree alcohol -> aldehyde

aldehyde

alcohol 1* degree

alcohol 2* degree

1) KMnO4 or Na2Cr2O7/acid/water or CrO3/acid/water or PCC

- turns OH to O with double bond
- 2-degree alcohol -> ketone

ketone

ROOR

Peroxide

1) PCC 2) 1)KMnO4 or Na2Cr2O7/acid/water or CrO3/acid/water

1 degree alcohol -> aldehyde -> carboxylic acid

carboxylic acid

R-COOH

1) OsO4 2)H2O2 or NaHSO3

1) Ozone 2) Zn, acetic acid

cleavage of the entire C=C, add O at the end
- 1 carbon is 3 degrees, the other is 2 with a Hydrogen

1) KMnO4 (hot) 2) H3O+, H2O

cleavage of the entire C=C, add O at the end
- 1 carbon is 3 degrees, the other is 2 with an OH group

1) HX, dark, cold, no peroxides (X = Cl, Br or I)
2) HX, dark, cold, no peroxides

- first one breaks triple bond to double bond and adds X in Markovnikov way
- second one breaks double bond to single bond and adds another X in Markovnikov way

1) X2
2) X2 (excess)

- first one breaks triple bond to double bond and adds 2 Xs in a trans way
- second one breaks double bond to single bond and adds another 2 Xs in a trans way

1) H2O, H2SO4, HgSO4

turns C(triple bond)C to O=C-CH3

permanganate

MnO4-

H2SO4, H2O

turns C(triple bond)N to O=C-OH

H2O2, NaOH, H2O

tautomerizes

HX

replaces Oh group with X, has a step in between that shows the X- (X as an anion)

SOCl2

replaces OH group with Cl

PBr3

replaces OH group with Br

Any nucleophile

replaces leaving group with Nuc

NaOH or KOH

replaces leaving group with OH

Na metal + alcohol (ROH) = NaOR

replaces leaving group with OR

NaNH2 + any molecule with a LG

replaces leaving group with the carbon anion

Cl2+ light (hv)

creates two products of one Cl on the least substituted carbon and one Cl on the most substituted carbon

Br2 + light (hv)

creates 1 product of Br on the most substituted carbon + HBr

radical initiator (NBS/heat or Br2/light) + Br2

Addition of 1 Br on the carbon NEXT to the double bond
Does not break double bond

Br2, Cold, dark, no peroxides

trans addition of 2 Br,
Breaks double bond

radical initiator (benzoyl peroxide) + HBr

Anti-addition of Br
Breaks double bond

HBr, Cold, dark, no peroxides

Markov addition of Br
Breaks double bond