Kinamycin F

Part 1 of 3

Br₂

AcOH
120 °C, 20 min

Selectivity : 66:33

MeOCH₂Cl, i-Pr₂NEt

CH₂Cl₂
0 °C, 30 min, 50 % (2 steps)

Also isolated was the C7-bromo product (33 % yield).

Na₂CO₃

MeOH
65 °C, 30 min, 96 %

Part 2 of 3

NH₃, t-BuOH, THF
-78 to -33 °C, 45 min, 100 %

See the Birch Reduction

AD-mix β, MsNH₂

TBME, t-BuOH, H₂O
12 °C, 40 h, 55 %

Selectivity : 83:17 er
See the Sharpless Asymmetric Dihydroxylation

2,2-Dimethoxypropane, Pyr^.TsOH

DMF
RT, 60 min, 88 %

CsF, PhSeCl

DMF
-50 °C, 80 min, 69 %

H₂O₂, Pyr

CH₂Cl₂
RT, 15 min, 83 %

Cristallized twice to 99:01 er.

TMSCH₂MgCl, CuI, TMSCl, Et₃N

THF, HMPA
-78 °C to RT, 2 h

See the Michael Addition

Pd(OAc)₂

MeCN
RT, 3 h, 88 % (2 steps)

See the Saegusa Oxidation

Part 3 of 3

TASF

CH₂Cl₂
-78 °C, 5 min, 79 %

See the Michael Addition

Pd(OAc)₂, Ph₃P, Ag₂CO₃

PhMe
80 °C, 60 min, 66 %

See the Heck Coupling

TfN₃, i-Pr₂NEt

MeCN
RT, 20 min, 99 %

TIPSOTf, i-Pr₂NEt

CH₂Cl₂
0 °C, 20 min

DMDO

CH₂Cl₂, MeOH
-40 °C, 15 min, 76 % (2 steps)

See the Rubottom Oxidation

BH₃^.THF

THF
-78 to -20 °C, 2 h, 58 %

HCl

MeOH
-12 to 0 °C, 7 h, 65 %