Abstract
3-Benzyl-4-isopropyl-2(5H )-furanone,
which is a precursor to two naturally-occurring cytotoxic (Z )-5-ylidene-2(5H )-furanone
derivatives, has been conveniently prepared from 3,4-dibromo-2(5H )-furanone by a three-step procedure
involving two Pd-catalyzed cross-coupling reactions and a Rh(I)-catalyzed
hydrogenation.
Key words
2(5H )-furanones - cross-coupling - regioselectivity - Stille reaction - benzylation
References
<A NAME="RZ12302SS-1">1 </A>
Rossi R.
Bellina F.
Raugei E.
Synlett
2000,
1749
<A NAME="RZ12302SS-2">2 </A>
Bellina F.
Anselmi C.
Rossi R.
Tetrahedron
Lett.
2002,
43:
2023
<A NAME="RZ12302SS-3">3 </A>
Bellina F.
Anselmi C.
Viel S.
Mannina L.
Rossi R.
Tetrahedron
2001,
57:
9997
<A NAME="RZ12302SS-4">4 </A>
Bellina F.
Anselmi C.
Rossi R.
Tetrahedron
Lett.
2001,
42:
3851
<A NAME="RZ12302SS-5">5 </A>
Ortega MJ.
Zubía E.
Ocaña JM.
Naranjo S.
Salvá J.
Tetrahedron
2000,
56:
3963
<A NAME="RZ12302SS-6">6 </A>
Evidente A.
Randazzo G.
Ballio A.
J.
Nat. Prod.
1986,
49:
593
For reviews on the synthesis of
stereodefined 5-ylidene-2(5H )-furanones,
see:
<A NAME="RZ12302SS-7A">7a </A>
Negishi E.-I.
Kotora M.
Tetrahedron
1997,
53:
6707
<A NAME="RZ12302SS-7B">7b </A>
Brückner R.
Curr. Org. Chem.
2001,
5:
679
<A NAME="RZ12302SS-7C">7c </A>
Brückner R.
Chem. Commun.
2001,
141
<A NAME="RZ12302SS-7D">7d </A>
Rossi R.
Bellina F.
Targets in Heterocyclic Systems:
Chemistry and Properties
2002,
5:
169
<A NAME="RZ12302SS-8">8 </A>
Bellina F.
Rossi R.
; Abstracts from Transmediterranean Colloquium
on Heterocyclic Chemistry;
Bari Italy June 20-24:
2002.
<A NAME="RZ12302SS-9">9 </A>
Yang X.
Shimizu Y.
Steiner JR.
Clardy J.
Tetrahedron Lett.
1993,
34:
761
<A NAME="RZ12302SS-10">10 </A>
Boukouvalas J.
Maltais F.
Lachance N.
Tetrahedron
Lett.
1994,
35:
7897
<A NAME="RZ12302SS-11">11 </A> This compound was prepared according
to a procedure reported in the literature:
Snyder HR.
Kuch JA.
Johnson JR.
J. Am. Chem. Soc.
1938,
60:
105
<A NAME="RZ12302SS-12">12 </A>
Ngwe H.
Nakayama E.
Higashi T.
Kinoshita H.
Inomata K.
Chem.
Lett.
1995,
713
<A NAME="RZ12302SS-13">13 </A>
It should be noted that when we attempted
to prepare 8a by hydrogenation of 18 in toluene at r.t. in the presence of
10 mol% Pd on BaSO4 , the reaction provided significant amounts
of a compound which had a MS spectrum corresponding to that of 4-isopropyl-2(5H )-furanone.
<A NAME="RZ12302SS-14">14 </A>
The catalyst precursor constiting
of Pd2 (dba)3 (2.5 mol%)/(o -Tol)3 P (10 mol%)
gave a similar yield, while the use of Pd2 (dba)3 (2.5
mol%)/Ph3 As (10 mol%) or Pd(PPh3 )4 (5 mol%)
as catalyst precursors gave less satisfactory results.
For previous examples of Pd-catalyzed
reactions between Csp
2 -hybridized
halides and benzylzinc halides, see:
<A NAME="RZ12302SS-15A">15a </A>
Negishi E.-i.
Tan Z.
Liou S.-Y.
Liao B.
Tetrahedron
2000,
56:
10197
<A NAME="RZ12302SS-15B">15b </A>
Gundersen L.-L.
Langli G.
Rise F.
Tetrahedron
Lett.
1995,
36:
1945
<A NAME="RZ12302SS-15C">15c </A>
Gundersen L.-L.
Bakkestuen AK.
Aasen J.
Overas H.
Rise F.
Tetrahedron
1994,
50:
9743
<A NAME="RZ12302SS-15D">15d </A>
Moriya T.
Miyaura N.
Suzuki A.
Chem.
Lett.
1993,
1429
<A NAME="RZ12302SS-15E">15e </A>
Negishi E.-i.
King AO.
Okukado N.
J.
Org. Chem.
1977,
42:
1821
<A NAME="RZ12302SS-16">16 </A>
It should be noted that the crude
product, derived from the Pd-catalyzed reaction of 8a with 20 , contained compound 14 and
significant amounts of 1,2-diphenylethane (22 )
and a compound which had a MS spectrum in agreement with that of
3,5-dibenzyl-4-isopropyl-2(5H )-furanone. The
use of PdCl2 [(o -Tol)3 P]2 (5
mol%)/CuI (10 mol%), Pd2 (dba)3 (2.5
mol%)/Ph3 As (10 mol%)/CuI
(10 mol%) or Pd2 (dba)3 (2.5 mol%)/t -Bu3 P (10 mol%)/CuI
(10 mol%) as catalyst precursors in NMP at 85 °C
gave less satisfactory results, while employing Pd2 (dba)3 (2.5
mol%)/t -Bu3 P
(10 mol%) as a catalyst precursor in dioxane at reflux
and in the presence of 3 equiv of KF no product was obtained.
<A NAME="RZ12302SS-17A">17a </A>
Chuang C.
Gallucci JC.
Hart DJ.
Hoffmann C.
J. Org.
Chem.
1988,
53:
3218
<A NAME="RZ12302SS-17B">17b </A>
Labadie JW.
Tueting D.
Stille JK.
J. Org. Chem.
1983,
48:
4634
<A NAME="RZ12302SS-18">18 </A>
Desponds O.
Schlosser M.
J. Organomet. Chem.
1991,
409:
93