Abstract
Aldol derivatives have been synthesized by redox-neutral catalytic
anti-Markovnikov hydration of propargyloxy substrates. A reiterative
sequence of aldehyde alkynylation and alkyne hydration leads to
1,3-polyol derivatives.
Key words
addition reactions - aldehydes - alkynes - homogeneous catalysis - ruthenium
References and Notes
1a Schneider C.
Angew. Chem. Int. Ed.
1998,
37:
1375
1b Oishi T.
Nakata T.
Synthesis
1990,
635
2 Burns NZ.
Baran PS.
Hoffmann RW.
Angew. Chem. Int. Ed.
2009,
48:
2854
3a Kondekar NB.
Kumar P.
Org. Lett.
2009,
11:
2611
3b Binder
JT.
Kirsch SF.
Chem.
Commun.
2007,
4164
3c Kumar P.
Gupta P.
Naidu SV.
Chem.
Eur. J.
2006,
12:
1397
3d Bode SE.
Wolberg M.
Müller M.
Synthesis
2006,
557
3e Tosaki S.
Horiuchi Y.
Nemoto T.
Ohshima T.
Shibasaki M.
Chem.
Eur. J.
2004,
10:
1527
3f Hoffmann RW.
Angew. Chem. Int. Ed.
2003,
42:
1096
3g Enders D.
Hundertmark T.
Tetrahedron Lett.
1999,
40:
4169
3h Rychnovsky SD.
Chem. Rev.
1995,
95:
2021
4 Trost BM.
Angew.
Chem., Int. Ed. Engl.
1995,
34:
259
5 Modern
Aldol Reactions
Mahrwald R.
Wiley-VCH;
Weinheim:
2004.
6 Hayashi Y.
Samanta S.
Itoh T.
Ishikawa H.
Org. Lett.
2008,
10:
5581
7a Tokunaga M.
Wakatsuki Y.
Angew.
Chem. Int. Ed.
1998,
37:
2867
7b Suzuki T.
Tokunaga M.
Wakatsuki Y.
Org.
Lett.
2001,
3:
735
8a Grotjahn DB.
Incarvito CD.
Rheingold AL.
Angew.
Chem. Int. Ed.
2001,
40:
3884
8b Grotjahn DB.
Lev DA.
J.
Am. Chem. Soc.
2004,
126:
12232
9 Labonne A.
Kribber T.
Hintermann L.
Org.
Lett.
2006,
8:
5853
10 Hintermann L.
Labonne A.
Synthesis
2007,
1121
11 The idea of synthesizing aldols in
this way has been expressed by others, see ref. 8b and ref. 14.
12 Trost BM.
Ball ZT.
Jöge T.
Angew.
Chem. Int. Ed.
2003,
42:
3415
13a Anand NK.
Carreira EM.
J. Am. Chem. Soc.
2001,
123:
9687
13b Sasaki H.
Boyall D.
Carreira EM.
Helv. Chim.
Acta
2001,
84:
964
14 Alvarez P.
Bassetti M.
Gimeno J.
Mancini G.
Tetrahedron Lett.
2001,
42:
8467
15 Hydration experiments with IndRuCl(PPh3 )2 were
attempted in either i -PrOH-H2 O
or an aqueous micellar system, with several alkynes. GC-MS analysis
usually revealed the presence of starting alkyne. Among minor reaction
products, we found traces of 2-octanone and heptene (from 1-octyne), and
products of alkyne trimerization. In addition, decomposition of
the ruthenium complex to indene and Ph3 P was observed
and tenside decomposition products (dodecanol, dodecene, chlorododecane
from sodium dodecyl sulfate).
16 Suzuki T.
Tokunaga M.
Wakatsuki Y.
Tetrahedron
Lett.
2002,
43:
7531
17 See the Supporting Information for
experimental details and additional information.
18a Datta S.
Chang C.-L.
Yeh K.-L.
Liu R.-S.
J.
Am. Chem. Soc.
2003,
125:
9294
18b Shen H.
Su H.
Hsueh Y.
Liu R.
Organometallics
2004,
23:
4332
18c D’Alessandro N.
Di Deo M.
Bonetti M.
Tonucci L.
Morvillo A.
Bressan M.
Eur. J.
Inorg. Chem.
2004,
810
19 Grotjahn DB.
Chem.
Eur. J.
2005,
11:
7146
20 Chevallier F.
Breit B.
Angew. Chem. Int. Ed.
2006,
45:
1599
21 Hintermann L.
Dang TT.
Labonne A.
Kribber T.
Xiao L.
Naumov P.
Chem. Eur. J.
2009,
15:
7167
22 Kribber T.
Labonne A.
Hintermann L.
Synthesis
2007,
2809
23 Labonne A.
Zani L.
Hintermann L.
Bolm C.
J. Org. Chem.
2007,
72:
5704
24 Catalyst loadings of 3 mol% gave
conversions of only
25 A solvent screen had indicated the
superiority of acetone over i -PrOH, EtOH,
MeOH, and THF.
26 See the Supporting Information for
experimental data.
27 Abe SJ.
J.
Chem. Soc. Jpn.
1937,
58:
246
28a Sabitha G.
Gopal P.
Yadav JS.
Synth. Commun.
2007,
37:
1495
28b Touati R.
Ratovelomanana-Vidal V.
Ben Hassine B.
Genet J.-P.
Tetrahedron:
Asymmetry
2006,
17:
3400
29a Drewes SE.
Sehlapelo BM.
Horn MM.
Scott-Shaw R.
Sandor P.
Phytochemistry
(Elsevier)
1995,
38:
1427
29b Andrianaivoravelona JO.
Sahpaz S.
Terreaux C.
Hostettmann K.
Stoeckli-Evans H.
Rasolondramanitra J.
Phytochemistry
(Elsevier)
1999,
52:
265
29c Tosaki S.
Horiuchi Y.
Nemoto T.
Ohshima T.
Shibasaki M.
Chem.
Eur. J.
2004,
10:
1527
30 Macro J.
Carda M.
Murga J.
Falomir E.
Tetrahedron
2007,
63:
2929
31a Garcia AB.
Leßmann T.
Umarye JD.
Mamane V.
Sommer S.
Waldmann H.
Chem. Commun.
2006,
3868
31b Umarye JD.
Leßmann T.
García AB.
Mamane V.
Sommer S.
Waldmann H.
Chem. Eur.
J.
2007,
13:
3305
32 These conditions are characterized
by use of the reaction medium acetone-H2 O (4:1)
and will be discussed elsewhere.
33 Cho SH.
Chang S.
Angew. Chem.
2007,
46:
1897
34 The Supporting Information to this
article contains experiment descriptions, analytical data, and additional information.
