Synthesis of Brasilenyne

Structure of Brasilenyne

C15H19ClO

Principal investigator	Scott E. Denmark
Publication year	2002
Synthesis type	Total
Number of steps	20 (linear)
References	J. Am. Chem. Soc. 2002, 124, 15196. J. Am. Chem. Soc. 2004, 126, 12432.

Part 1 of 1

intermediate structure

BF3.OEt2, EtCHO

Et2O

-30 to 0 °C, 2 h, 85%

intermediate structure

BH3.THF

THF

0 °C, 3 h, 82%

intermediate structure

Pyr, TBSCl

CH2Cl2

RT, 4 h, 85%

intermediate structure

Special reagent

TiCl4

CH2Cl2

-72 °C, 3 h

intermediate structure

TsOH

Dean-Stark

PhH

Reflux, 1 h, 86% (2 steps)

See the Fischer-Speier Esterification

intermediate structure

AgNO3, NIS

DMF

RT, 10 min, 95%

intermediate structure

AcOH, KO2C-N=N-CO2K

i-PrOH, THF

RT, 5 h, 80%

intermediate structure

AlMe3, NHMeOMe.HCl

CH2Cl2

0 °C to RT, 2 h, 93%

intermediate structure

Ag2O, (4-MeOPh)CH2Cl

CH2Cl2

RT, 24 h, 82% (89% BRSM)

intermediate structure

i-Bu2AlH

CH2Cl2

-73 °C, 3 h, 87%

intermediate structure

Special reagent

Et2O

-100 °C, 2 h, 89%

See the Brown Asymmetric Allylation

intermediate structure

Special reagent

Et3N

CH2Cl2

0 °C to RT, 30 min, 91%

intermediate structure

Special reagent

PhH

RT, 1 h, 92%

See the Olefin Metathesis

intermediate structure

n-Bu4N+ F-, (n3-C3H3PdCl)2

THF

RT, 61 h, 61%

See the Hiyama Coupling

intermediate structure

DMAP, Pyr, TBSOTf

CH2Cl2

0 °C to RT, 2 h, 88%

intermediate structure

DDQ

CH2Cl2, H2O

RT, 30 min, 84%

intermediate structure

Dess-Martin Periodinane

CH2Cl2

RT, 2 h, 83%

See the Dess-Martin Oxidation

intermediate structure

Special reagent

n-BuLi

THF

-74 °C to RT, 8.5 h, 71%

See the Peterson Olefination

"Also isolated was the E-isomer (12%)"

intermediate structure

n-Bu4N+ F-

THF

0 °C, 90 min, 93%

intermediate structure

CCl4, n-Oct3P

PhMe

RT to 65 °C, 12.5 h, 925

See the Appel Reaction

intermediate structure

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