TETRAHEDRON
LETTERS
Pergamon Tetrahedron Letters 40 (1999) 1187-1190
Synthesis of erythro and threo Furanoid Glycals Using 5-
endo.trig Selenoetherification as Key Step
Fernando Bravo, Mohamed Kassou, Sergio Castill6n*
Departament de Qu(mica Anal(tica i Quimica Orgfznica, UniversitatRovira i Virgili, Pea. Imperial Tarraco, 1.
43005 Tarragon&Spain
Received 2 October 1998; revised 25 November 1998; accepted 30 November 1998
Abstract
Differently protected erythro and threo furanoid glycals were synthesised from 4-pentene-l,2,3-triol, through
selenium induced 5-endo-trig cyclization and selenoxide elimination. © 1999 Elsevier Science Ltd. All rights reserved.
The use of glycals as important glycosyl donors has been extensively discussed in the
literature.' Indeed, a number of recent articles describe them as important precursors of
oligosaccharides,2 C-glycosides3 and C-nucleosides,' nucleosides5 and others. 6-8 Both pyranoid
and furanoid glycals are usually obtained by reductive elimination of appropriately activated
compounds. Ireland's method, 9 which starts from 1-halo-2,3-O-isopropylidenefuranoses and
Li/NH3(1) as reducing agent, has been widely used for the synthesis of differently protected
furanoid glycals of erythro configuration (Scheme l, via a). Some of the drawbacks of this
method are that many useful protecting groups are not stable in the strongly reducing
conditions of the reaction, and that glycals of threo configuration require a long multistep
synthesis.
In attempts to overcome these limitations, several new procedures based on elimination
reactions from 1-O-mesyl furanoses 1° (Scheme l, via b, X=OMs), or thymidine1~ (Scheme l,
Scheme 1
RO
RO
ductive
ination
9
RO I~-0,,~ x ' - - 1 . .b .. ~ I ROT
l ellminallon I L--- o
OR' X=OMs ref. 10 [
X= ~-Thy ref. 11 [
X= Se(O)Ph ref. 14 I., glyCal
~roxylation
R O ~ o H J ref. 12
OR'OH
OH
. OR'
T'
~,.a... ~,r-2 -~.s°:d
OR i~ h
0040-4039/99/$ - see front matter © 1999 Elsevier Science Ltd. All rights reserved.
PH: S0040-4039(98 )02562-3