Synthesis of Longifolene

Longifolene H3C
CH3
C

H3C

 A naturally occurring, oily liquid hydrocarbon found

primarily in the high-boiling fraction of certain pine resins.

 The name is derived from that of a pine species from which

the compound was isolated, Pinus longifolia.

 Compact tricyclic structure and lack of functional groups.

 Attractive target for research groups highlighting new

synthetic methodologies.

 Notable syntheses are by Corey, McMurray, Johnson, 

Oppolzer, and Schultz.
Retrosynthesis
Longifolene
 Retrosynthesis

Me O
Me OR O
O

Me
O O O
O

W. Oppolzer, T. Godel, J. Am. Chem. Soc. 1978, 100, 2583 –

2584
 O
O
Et3N
N Cl
+ CHCl3
O 35 oC, 82 % O
1

O OCBz OCBz
ClCO2Bn

Pyr
O 5 oC, 8 h, 88 % O
2 O
 De Mayo reaction
OCBz
OCBz
hv
Cyclohexane
15-30 oC, 83 % O
O 3
 O
OCBz
H2, Pd/C
3 atm
AcOH
RT, 18 h, 83 %
O O
3 4

Ph3P+CH3 Br-, NaOt-Amyl

PhMe
RT, 90 min, 88 %
O O
4 5
 Zn-Cu, CH2I2

Et2O
O Reflux, 60 h, 78 % O
5 6
H3C
CH3
H2, PtO2
3 atm

AcOH
RT, 18 h, 96 %
O O 7
6
H3C H3C
CH3 CH3
i. i-Pr2NLi
ii. MeI

THF H3C
o
-78 C to RT, 2 h, 94 %
O 7 O
8

H3C H3C
CH3 CH3

MeLi

H3C Et2O H3C

48 oC, 3 h HO
O CH3
8 9
 H3C H3C
CH3 CH3

SOCl2

H3C Pyr H3C

HO 0 oC, 10 min, 80 %
CH3 10
9