tant reactions of this type.
These reactions occur mostly onthe singlet hypersurface and deliver the respective photo-products stereospecifically.
] Photocyclizations can be classified according to thetype of substrate that is employed. The majority of thesereactions involve 1,3,5-trienes (
) to generate carbocycles, orenamides (
) to afford heterocyclic products (Figure 1).Substrates of type
are less common and,in the case of X
NR, can be used for the synthesis of pyrrolines, dihydroindoles, and hexahydrocarbazoles. Oneexample of this type of reaction is the cyclization of tertiaryenaminone
to generate tricyclic
] ring closure results in theformation of zwitterion
as an intermediate, which thenundergoes a suprafacial 1,4-H shift to afford the product. Thisreaction has been exploited in the synthesis of indolealkaloids. In the present case, the photoproduct was con-verted in twelve steps into (
the reduction of which is known to generate (
) (Scheme 2).
Another application of the cyclization of a substrate of class
can be found in the synthesis of (
Inthis example, a vinyl aryl ether (Figure 1; structure
O)rather than an amine served as the substrate for the photo-reaction.
] Photocyclization of Trienes
A recent synthesis by Moses and co-workers nicelyillustrates the stereochemical course of the [6
The natural product (
) wasobtained from
, in what is believed to be abiomimetic reaction (Scheme 3).The correct relative configuration of the two adjacentstereogenic centers was established by a conrotatory ringclosure. The synthesis of substrate
was achieved by a Suzukicross-coupling reaction of a dienylboronate and an alkenylbromide attached to a
)-iso-9,10-deoxytridachione were also synthesized by abiomimetic photocyclization from an analogous tetraene
Thorsten Bach studied chemistry at the Uni-versität Heidelberg and at the University of Southern California (G. A. Olah). Heobtained his PhD in 1991 from the Universi-tät Marburg (M. T. Reetz). After a postdoc-toral stay at Harvard University (D. A.Evans), his independent research career led him via the Universität Münster (1992– 1996) and the Universität Marburg (1997– 2000) to the Technische Universität Mün-chen, where he has been ever since. Since2006 he has been an elected member of theGerman Academy of Sciences (Leopoldina)and since 2009 of the Bavarian Academy of Sciences. Jörg P. Hehn studied chemistry at the Uni-versität Würzburg, University of Cambridge(UK), and the Universität Marburg, wherehe carried out his diploma thesis under thesupervision of U. Koert in 2007. After aresearch internship at Actelion Pharmaceut-icals Ltd. in Allschwil (CH), he joined thegroup of T. Bach, where he is working towards his PhD on the [2
2] photocycload-dition of tetronates and the application of this reaction to natural product synthesis.
General representation of substrates
for the [6
The initial [6
] photocyclization of enaminone
used in theformal synthesis of (
] cyclization to afford (
T. Bach and J. P. Hehn
2011 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Angew. Chem. Int. Ed.