Tandem Olefin Migration-Aldol Condensation in Water with an Amphiphilic Resin-Supported Ruthenium Complex

Abstract

A catalytic tandem olefin migration-aldol condensation process with allylic carbinols and aryl aldehydes was performed with 0.5 mol% of an amphiphilic polystyrene-poly(ethylene glycol) (PS-PEG) resin supported phosphine-ruthenium complex in water as a single reaction medium under heterogeneous conditions to give the corresponding aldols with syn selectivity. Inverse stereoselectivity (anti selectivity) was observed when the reaction was carried out in the presence of K₂CO₃.

tandem reaction - aldol condensation - aqueous media - polymer support - ruthenium catalyst

References and Notes

1

Present address: Graduate School Division of Engineering, Doshisha University; [e-mail].

For reviews on aqueous switching of organic transformations, see:

2a Li C.-J. Chan T.-H. Organic Reactions in Aqueous Media   Wiley-VCH; New York: 1997. 

2b Grieco PA. Organic Synthesis in Water   Kluwer Academic Publishers; Dordrecht: 1997. 

2c Herrmann WA. Kohlpaintner CW. Angew. Chem., Int. Ed. Engl.  1993,  32:  1524 

2d Lindström UM. Chem. Rev.  2002,  102:  2751 

2e Commentary: Uozumi Y. Synlett  2010,  1988 

For reviews on heterogeneous switching of organic transformations, see:

3a Bailey DC. Langer SH. Chem. Rev.  1981,  81:  109 

3b Shuttleworth SJ. Allin SM. Sharma PK. Synthesis  1997,  1217 

3c Shuttleworth SJ. Allin SM. Wilson RD. Nasturica D. Synthesis  2000,  1035 

3d Dörwald FZ. Organic Synthesis on Solid Phase   Wiley-VCH; Weinheim: 2000. 

3e Leadbeater NE. Marco M. Chem. Rev.  2002,  102:  3217 

3f Ley SV. Baxendale IR. Bream RN. Jackson PS. Leach AG. Longbottom DA. Nesi M. Scott JS. Storer RI. Taylor SJ. J. Chem. Soc., Perkin Trans. 1  2000,  3815 

3g McNamara CA. Dixon MJ. Bradley M. Chem. Rev.  2002,  102:  3275 

3h Chiral Catalyst Immobilization and Recycling   De Vos DE. Vankelecom IFJ. Jacobs PA. Wiley-VCH; Weinheim: 2000. 

3i Fan Q.-H. Li Y.-M. Chan ASC. Chem. Rev.  2002,  102:  3385 

3j Uozumi Y. Top. Curr. Chem.  2004,  242:  77 

3k Guino M. Hii KKM. Chem. Soc. Rev.  2007,  36:  608 

3l Wang Z. Chen G. Ding K. Chem. Rev.  2009,  109:  322 

3m Lu J. Toy PH. Chem. Rev.  2009,  109:  815 

4a Bayer E. Rapp W. In Chemistry of Peptides and Proteins   Vol. 3:  Voelter W. Bayer E. Ovchinikov YA. Iwanov VT. Walter de Gruter; Berlin: 1986.  p.3 

4b Rapp W. In Combinatorial Peptide and Nonpeptide Libraries   Jung G., VCH; Weinheim: 1996.  p.425 

For studies on polymer-supported transition-metal-complex catalysts from the author’s group, see for allylic substitution:

5a Uozumi Y. Danjo H. Hayashi T. Tetrahedron Lett.  1997,  38:  3557 

5b Danjo H. Tanaka D. Hayashi T. Uozumi Y. Tetrahedron  1999,  55:  14341 

Cross-coupling:

5c Uozumi Y. Danjo H. Hayashi T.
J. Org. Chem.  1999,  64:  3384 

Carbonylation reaction:

5d Uozumi Y. Watanabe T. J. Org. Chem.  1999,  64:  6921 

Suzuki-Miyaura coupling:

5e Uozumi Y. Nakai Y. Org. Lett.  2002,  4:  2997 

Heck reaction:

5f Uozumi Y. Kimura T. Synlett  2002,  2045 

Asymmetric alkylation:

5g Uozumi Y. Shibatomi K. J. Am. Chem. Soc.  2001,  123:  2919 

Asymmetric amination:

5h Uozumi Y. Tanaka H. Shibatomi K. Org. Lett.  2004,  6:  281 

Asymmetric catalysis:

5i Hocke H. Uozumi Y. Synlett  2002,  2049 

Rh catalysis:

5j Uozumi Y. Nakazono M. Adv. Synth. Catal.  2002,  344:  274 

Asymmetric catalysis:

5k Hocke H. Uozumi Y. Tetrahedron  2003,  59:  619 

5l Hocke H. Uozumi Y. Tetrahedron  2004,  60:  9297 

Asymmetric cycloisomerization:

5m Nakai Y. Uozumi Y. Org. Lett.  2005,  7:  291 

Cross-coupling:

5n Uozumi Y. Kikuchi M. Synlett  2005,  1775 

Asymmetric etherification:

5o Uozumi Y. Kimura M. Tetrahedron: Asymmetry  2006,  17:  161 

Asymmetric alkylation:

5p Kobayashi Y. Tanaka D. Danjo H. Uozumi Y. Adv. Synth. Catal.  2006,  348:  1561 

Allylic azidation:

5q Uozumi Y. Suzuka T. Kawade R. Takenaka H. Synlett  2006,  2109 

Nitromethylation:

5r Uozumi Y. Suzuka T. J. Org. Chem.  2006,  71:  8644 

Allylic sulfonylation:

5s Uozumi Y. Suzuka T. Synthesis  2008,  1960 

Asymmetric desymmetrization:

5t Uozumi Y. Takenaka H. Suzuka T. Synlett  2008,  1557 

Asymmetric Suzuki coupling:

5u Uozumi Y. Matsuura Y. Arakawa T. Yamada YMA. Angew. Chem. Int. Ed.  2009,  48:  2708 

Pt-catalyzed oxidation:

5v Yamada YMA. Arakawa T. Hocke H. Uozumi Y. Chem. Asian J.  2009,  4:  1092 

Sonogahsira coupling:

5w Suzuka T. Okada Y. Ooshiro K. Uozumi Y. Tetrahedron  2010,  66:  1064 

Buchwald-Hartwig reaction:

5x Hirai Y. Uozumi Y. Chem. Commun.  2010,  46:  1103 

5y Hirai Y. Uozumi Y. Chem. Asian J.  2010,  5:  1788 

6 Kharasch reaction: Oe Y. Uozumi Y. Adv. Synth. Catal.  2008,  350:  1771 

For examples of amphiphilic polymer-supported ruthenium complexes, see:

7a Kayaki Y. Shimokawatoko Y. Ikariya T. Adv. Synth. Catal.  2003,  345:  175 

7b Judkins CMG. Knights KA. Johnson BFG. De Miguel YR. Raja R. Thomas JM. Chem. Commun.  2001,  2624 

In water:

8a Wang M. Li CJ. Tetrahedron Lett.  2002,  43:  3589 

In ionic liquid:

8b Yang X.-F. Wang M. Varma RS. Li C.-J. Org. Lett.  2003,  5:  657 

In aqueous organic media:

8c Wang M. Yang X.-F. Li C.-J. Eur. J. Org. Chem.  2003,  998 

8d Yang X.-F. Wang M. Varma RS. Li C.-J. J. Mol. Catal. A: Chem.  2004,  214:  147 

Rh catalysis:

9a Gazzard LJ. Motherwell WB. Sandham DA. J. Chem. Soc., Perkin Trans. 1  1999,  979 

Fe:

9b Crévisy N. Wietrich M. Le Boulaire V. Uma R. Grée R. Tetrahedron Lett.  2001,  42:  395 

9c Uma R. Gouault N. Crévisy N. Grée R. Tetrahedron Lett.  2003,  43:  6187 

Ni:

9d Cuperly D. Crévisy N. Grée R. Synlett  2004,  93 

9e Cuperly D. Petrignet J. Crévisy N. Grée R. Chem. Eur. J.  2006,  12:  3261