Abstract
Asymmetric direct aldol reaction of trifluoromethylacetaldehyde
with aldehyde using diarylprolinol as a catalyst, to afford a synthetically
useful β-trifluoromethyl-β-hydroxy aldehyde with excellent
enantioselectivity, was developed. Commercially available trifluoromethylacetaldehyde
ethyl hemiacetal was used directly as a precursor of trifluoromethylacetaldehyde
without acid pyrolysis or distillation prior to use.
Key words
asymmetric synthesis - aldol reactions - organocatalyst - diarylprolinol - trifluoromethylacetaldehyde
References and Notes
1a
Enantiocontrolled Synthesis of Fluoro-Organic Compounds
Soloshonok VA.
Wiley;
Chichester:
1999.
1b
Kirsch P.
Modern Fluoroorganic Chemistry
Wiley-VCH;
Weinheim:
2004.
1c
Uneyama K.
Organofluorine Chemistry
Blackwell;
Oxford:
2006.
1d
Ojima I.
Fluorine in Medicinal Chemistry and Chemical Biology
Blackwell;
Oxford:
2009.
2 Review, see:
Modern
Aldol Reactions
Vol. 1 and 2:
Mahrwald R.
Wiley-VCH;
Weinheim:
2004.
3
Iseki K.
Oishi S.
Kobayashi Y.
Tetrahedron
1996,
52:
71
4
List B.
Lerner RA.
Barbas CF.
J.
Am. Chem. Soc.
2000,
122:
2395
For selected reviews on organocatalysis,
see:
5a
Dalko
PI.
Moisan L.
Angew.
Chem. Int. Ed.
2004,
43:
5138
5b
Asymmetric
Organocatalysis
Berkessel A.
Groger H.
Wiley-VCH;
Weinheim:
2005.
5c
Hayashi Y.
J.
Synth. Org. Chem. Jpn.
2005,
63:
464
5d
List B.
Chem. Commun.
2006,
819
5e
Marigo M.
Jørgensen KA.
Chem.
Commun.
2006,
2001
5f
Gaunt MJ.
Johansson
CCC.
McNally A.
Vo NT.
Drug
Discov. Today
2007,
12:
8
5g
Enantioselective
Organocatalysis
Dalko PI.
Wiley-VCH;
Weinheim:
2007.
5h
Mukherjee S.
Yang
JW.
Hoffmann S.
List B.
Chem. Rev.
2007,
107:
5471
5i
Walji AM.
MacMillan DWC.
Synlett
2007,
1477
5j
MacMillan DWC.
Nature (London)
2008,
455:
304
5k
Barbas CF.
Angew. Chem. Int. Ed.
2008,
47:
42
5l
Dondoni A.
Massi A.
Angew. Chem. Int. Ed.
2008,
47:
4638
5m
Melchiorre P.
Marigo M.
Carlone A.
Bartoli G.
Angew. Chem. Int. Ed.
2008,
47:
6138
5n
Bertelsen S.
Jørgensen KA.
Chem.
Soc. Rev.
2009,
38:
2178
6
Torii H.
Nakadai M.
Ishihara K.
Saito S.
Yamamoto H.
Angew.
Chem. Int. Ed.
2004,
43:
1983
7
Funabiki K.
Yamamoto H.
Nagaya H.
Matsui M.
Tetrahedron Lett.
2006,
47:
5507
8
Northrup AB.
MacMillan DWC.
J. Am.
Chem. Soc.
2002,
124:
6978
Selected examples of organocatalytic
cross-aldol reaction of aldehydes, see:
9a
Chowdari NS.
Ramachary DB.
Cordova A.
Tetrahedron Lett.
2002,
43:
9591
9b
Pihko
PM.
Erkkila A.
Tetrahedron
Lett.
2003,
44:
7607
9c
Pidathala C.
Hoang L.
Vignola N.
List B.
Angew. Chem. Int. Ed.
2003,
42:
2785
9d
Mase N.
Tanaka F.
Barbas CF.
Org. Lett.
2003,
5:
4369
9e
Mans DM.
Pearson WH.
Org.
Lett.
2004,
6:
3305
9f
Thayumanavan R.
Tanaka F.
Barbas FC.
Org. Lett.
2004,
6:
3541
9g
Northrup AB.
Mangion IK.
Hettche F.
MacMillan DWC.
Angew.
Chem. Int. Ed.
2004,
43:
2152
9h
Mase N.
Tanaka F.
Barbas CF.
Angew. Chem. Int. Ed.
2004,
43:
2420
9i
Mangion IK.
Northrup AB.
MacMillan DWC.
Angew. Chem. Int. Ed.
2004,
43:
6722
9j
Storer RI.
MacMillan DWC.
Tetrahedron
2004,
60:
7705
9k
Northrup AB.
Macmillan DWC.
Science
2004,
305:
1752
9l
Reyes E.
Cordova A.
Tetrahedron Lett.
2005,
46:
6605
9m
Casas J.
Engqvist M.
Ibrahem I.
Kaynak B.
Cordova A.
Angew.
Chem. Int. Ed.
2005,
44:
1343
9n
Cordova A.
Engqvist M.
Ibrahem I.
Casas J.
Sunden H.
Chem.
Commun.
2005,
2047
9o
Cordova A.
Ibrahem I.
Casas J.
Sunden H.
Engqvist M.
Reyes E.
Chem. Eur. J.
2005,
11:
4772
9p
Hayashi Y.
Aratake S.
Okano T.
Takahashi J.
Samiya T.
Shoji M.
Angew. Chem. Int. Ed.
2006,
45:
5527
9q
Hayashi Y.
Itoh T.
Aratake S.
Ishikawa H.
Angew. Chem. Int. Ed.
2008,
47:
2082
10
Hayashi Y.
Itoh T.
Aratake S.
Ishikawa H.
Angew. Chem. Int. Ed.
2008,
47:
2082
11
Urushima T.
Yasui Y.
Ishikawa H.
Hayashi Y.
Org. Lett.
2010,
12:
2966
12 TCI, catalog number T0791.
13 When the reaction was performed in
72 h, the yield increased to 49% but the anti /syn ratio decreased to 3.5:1, which indicates
that the partial isomerization occurred during the reaction.