Abstract
A major challenge in organic synthesis is the selective reaction of a functional group in the presence of others. This can be achieved by using an appropriate reagent, tuned to react exclusively at the desired center. An alternate approach would be to use a single reagent, and to transmit from the outside the information as to where it should react. This account describes the use of light as a controlling element; indeed, in addition to the intensity, changing the wavelength gives an additional handle to direct the chemoselectivity.
1 Introduction
2 Background
3 Initial Attempts
4 Energy Transfer
5 Photocleavable Linkers
6 Real Orthogonality
7 Photoacylation
8 Outlook
Key words
photochemistry - protecting groups - cleavage - chromophores
References
1a
Kohler B.
Krause JL.
Raksi F.
Wilson KR.
Yakovlev VV.
Whitnell RM.
Yan Y.
Acc. Chem. Res.
1995,
28:
133 ; this very inspiring article is entitled Controlling the Future of Matter
1b See also: Zare RN.
Science
1998,
279:
1875
2
Bochet CG.
Angew. Chem. Int. Ed.
2001,
40:
2071
3
Blanc A.
Bochet CG.
J. Org. Chem.
2002,
67:
5567
4
Bochet CG.
J. Chem. Soc., Perkin Trans. 1
2002,
125
5a
Patchornik A.
Amit B.
Woodward RB.
J. Am. Chem. Soc.
1970,
92:
6333
5b For a recent mechanistic study, see: Il’Ichev YV.
Schwörer MA.
Wirz J.
J. Am. Chem. Soc.
2004,
126:
4581
6
Bochet CG.
Tetrahedron Lett.
2000,
41:
6341
7a
Chamberlin JW.
J. Org. Chem.
1966,
31:
1658
7b
Pincock JA.
Acc. Chem. Res.
1997,
30:
43
7c
Zimmerman HE.
J. Am. Chem. Soc.
1995,
117:
8988 ; and references cited
8a
Peukert S.
Giese B.
J. Org. Chem.
1998,
63:
9045
8b
Glatthar R.
Giese B.
Org. Lett.
2000,
2:
2315
9
Kessler M.
Glatthar R.
Giese B.
Bochet CG.
Org. Lett.
2003,
5:
1179
10
Schelhaas M.
Waldmann H.
Angew. Chem., Int. Ed. Engl.
1996,
35:
2056
11a
Sheehan JC.
Wilson RM.
J. Am. Chem. Soc.
1964,
30:
5277
11b
Sheehan JC.
Wilson RM.
Oxford AW.
J. Am. Chem. Soc.
1971,
93:
7222
11c For more recent work, see: Rajesh CS.
Givens RS.
Wirz J.
J. Am. Chem. Soc.
2000,
122:
611 ; and references cited therein
12
Amit B.
Ben-Efraim DA.
Patchornik A.
J. Am. Chem. Soc.
1976,
98:
843
13a
Helgen C.
Bochet CG.
Synlett
2001,
1968
13b See also: Nicolaou KC.
Safina BS.
Winssinger N.
Synlett
2001,
900
14
Helgen C.
Bochet CG.
J. Org. Chem.
2003,
68:
2483
15 Helgen, C.; Bochet, C. G. manuscript in preparation.
16
Blanc A.
Bochet CG.
J. Org. Chem.
2003,
68:
1138