Synthetic Transformations: Straumanis OChem 1

1. Hg(OAc)2 , H 2 OTHF (solvent)
2. NaBH4

-Markov Addition of OH and H or R-Mercury prevents rearrangement-NaBH4 replaces HgOAc with an H or R in 2nd synthetic step

1) BH3, THF
2) H2O2, NaOH

- Anti- Markov. Addition of H and OH- if a ring, adds them in SYN

1. HBr, ROOR to alkene

- Anti- Markov. addition of H and Br

HX, no peroxides to an alkene in cold and dark

-Markov Addition of H and X

Br2

-Trans addition of Br2 to alkene
- 1st Br forms 3 member cyclic ring, opened by 2nd Br

MCPBA

-Oxidation of Alkene to epoxide
- remember that epoxides are highly strained, will give rise to trans products

1. H+, HOR

-markov epoxide ring opening (acidic conditions)
- trans because acid and base have to be added in 2 separate steps

1. Strong base
2. Dilute acid

-anti-markov epoxide ring opening (basic conditions)
-trans

1. Br2, HOR

- markov addition of Br and OR to alkene
-trans

1. H2, Pt0 or Pd0

- catalytic hydrogenation
-syn only

1. H2/ Pt or PD metal

-triple to single bond
-syn addition

1. H2/Ni2B or H2/Lindlar Catalyst

-triple to double bond in cis

1. Na0, NH3

-triple to double bond in trans

1. PCC

-Oxidation of 1° Alc to aldehyde
- takes off an H, adds double bond to O- Product CAN be oxidized to carboxylic acid

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

- Oxidation of 2° alc to ketone
-product CANNOT be oxidized to carboxylic acid (you'd have to break a C-C bond)

1. KMnO4 or Na2Cr2O7/acid/water or CrO3/acid/water

-oxidation of 1° to Carboxylic acid