Res. Chem. Intermed.
, Vol. 33, No. 3–5, pp. 297–309 (2007)
Also available online - www.brill.nl/rci
Semiconductor photocatalysis type B: synthesis of
unsaturated α-cyano-homoallylamines from imines and
oleﬁns photocatalysed by silica- and cellulose-supported
H. C. PEHLIVANUGULLARI, E. SUMER and H. KISCH
Universität Erlangen-Nürnberg, Institut für Anorganische Chemie,
Egerlandstrasse 1, D-91058 Erlangen, Germany
Received 28 October 2005; accepted 9 December 2005
Abstract—α-Cyano-homoallylamines are synthesised in moderate yields by the photocatalysed linear
addition of oleﬁns to Ph(CN)C=NPh in the presence of silica-supported cadmium sulphide. Band
edge positions of cadmium sulphide and the rate and diastereoselectivity of this radical C–C coupling
reaction are not signiﬁcantly changed when the semiconductor is supported onto cellulose. The latter
result is in accordance with the absence of covalent semiconductor–support interactions.
Keywords: Photocatalysis; semiconductor; α-cyano-homoallylamines;
Homoallyl amines are important starting or intermediate materials in the synthe-
sis of biologically active substances; for instance, for further transformations to
β-amino acids which are of interest especially in the synthesis of β-lactam antibi-
otics [1, 2]. They are also useful as resolving agents and chiral auxiliaries for asym-
metric reactions .
Homoallyl amines were previously synthesised by 1,2-nucleophilic addition of
allylic organometallic reagents to imines in the presence of Lewis acids [4, 5], by
reaction of N-acyl-α-methoxyamines with organozinc reagents , Ti(0)-induced
allylation of imines  and by Ritter reaction with cyclopropyl alcohols .
Different to the above multistep processes, the CdS-catalysed photo-addition of
oleﬁns and enol/allyl ethers to imines [9–14] has brought a new dimension to
homoallyl amine synthesis, since it is a one-step reaction and does not require
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