Tandem response

Tandem reaction using the example of a "zipper reaction".

Tandem reaction (also domino or cascade reaction , English zipper reaction ) is a generic term for an intramolecular reaction sequence of often highly reactive, acyclic precursors to complex, polynuclear molecules . This means overall reactions that actually consist of several independent reaction stages (not mechanistic steps) that take place spontaneously in immediate succession. They could also be carried out one at a time in order to arrive at the same product.

The educt of a tandem reaction usually contains several functional groups, all of which are converted into complex target molecules almost simultaneously in a sequence of chemical reactions.

The advantage of the tandem reaction lies in the speed of the reaction , which is often high due to its intramolecular nature. The selectivity is also high, since intermediate stages rarely have to be isolated, hardly any by-products are produced and physical separation steps can be minimized.

The active reaction centers in tandem reactions are diverse, e.g. B. active double or triple bond centers or epoxides.

A variety of reaction types can be used, such as Diels-Alder reactions , ring opening reactions, Heck reactions . or Pauson-Khand reactions .

A wide range of target molecules can be produced via tandem reactions, e.g. B. Polyether ladder polymers via oxirane tandem reactions, terpenoids, indoalkaloids and many other natural products .

Individual evidence

↑ ^a ^b Barry M. Trost and Yian Shi: A Pd-Catalyzed Zipper Reaction . In: J. Am. Chem. Soc. . 113, 1991, pp. 701-703. doi : 10.1021 / ja00002a064 .
↑ MM Abelman and LE Overman: Palladium-catalyzed polyene cyclizations of dienyl aryl iodides . In: J. Am. Chem. Soc. . 110, No. 7, 1988, pp. 2328-2329. doi : 10.1021 / ja00215a068 .
↑ T. Sugihara, C. Coperet, Z. Owczarczyk, LS Harring and E.-i. Negishi: Deferred Carbonylative Esterification in the Pd-Catalyzed Cyclic Carbometalation-Carbonylation Cascade . In: J. Am. Chem. Soc. . 116, No. 17, 1994, pp. 7923-7924. doi : 10.1021 / ja00096a070 .
↑ Ronald Grigg and Visuvanathar Sridharan: Heterocycles via Pd catalysed molecular queuing processes. Relay switches and the maximization of molecular complexity . In: Pure Appl. Chem. . 70, No. 5, 1998, pp. 1047-1057.
↑ Xiaomin Jin, Cook Group: Palladium Catalyzed Cyclization / Suzuki Coupling of 1,6-Enynes ( Memento from September 20, 2009 in the Internet Archive ) (February 11, 2005).
↑ Nakcheol Jeong, Byung Ki Sung Jin Sung Kim, Soon Bong Park, Sung Deok Seo Jin Young Shin, Kyu Yeol In, and Yoon Kyung Choi: Pauson- Khand-type reaction mediated by Rh (I) catalysts . In: Pure Appl. Chem. . 74, No. 1, 2002, pp. 85-91.
↑ Graham L. Simpson, Timothy P. Heffron, Estíbaliz Merino, and Timothy F. Jamison: Ladder Polyether Synthesis via Epoxide-Opening Cascades Using a Disappearing Directing Group . (Communication) In: J. Am. Chem. Soc. . 128, No. 4, 2006, pp. 1056-1057. doi : 10.1021 / ja057973p .

literature

Yifa Zhou: Enantioselective synthesis of the indoalkaloids of the Vallesiachotamine and Corynanthe types by Domino reaction . Cuvillier, ISBN 3897124033
Hans-Jürgen Gutke: Investigations on the anionically induced domino reaction - building blocks for the synthesis of terpenoids . Shaker Verlag GmbH, ISBN 3826574648
Palladium (II) -catalyzed domino reactions for enantioselective synthesis , by Florian Stecker (as Google Book)

[Trost-1] Barry M. Trost and Yian Shi: A Pd-Catalyzed Zipper Reaction . In: J. Am. Chem. Soc. . 113, 1991, pp. 701-703. doi : 10.1021 / ja00002a064 .

[2] MM Abelman and LE Overman: Palladium-catalyzed polyene cyclizations of dienyl aryl iodides . In: J. Am. Chem. Soc. . 110, No. 7, 1988, pp. 2328-2329. doi : 10.1021 / ja00215a068 .

[3] T. Sugihara, C. Coperet, Z. Owczarczyk, LS Harring and E.-i. Negishi: Deferred Carbonylative Esterification in the Pd-Catalyzed Cyclic Carbometalation-Carbonylation Cascade . In: J. Am. Chem. Soc. . 116, No. 17, 1994, pp. 7923-7924. doi : 10.1021 / ja00096a070 .

[4] Ronald Grigg and Visuvanathar Sridharan: Heterocycles via Pd catalysed molecular queuing processes. Relay switches and the maximization of molecular complexity . In: Pure Appl. Chem. . 70, No. 5, 1998, pp. 1047-1057.

[5] Xiaomin Jin, Cook Group: Palladium Catalyzed Cyclization / Suzuki Coupling of 1,6-Enynes ( Memento from September 20, 2009 in the Internet Archive ) (February 11, 2005).

[6] Nakcheol Jeong, Byung Ki Sung Jin Sung Kim, Soon Bong Park, Sung Deok Seo Jin Young Shin, Kyu Yeol In, and Yoon Kyung Choi: Pauson- Khand-type reaction mediated by Rh (I) catalysts . In: Pure Appl. Chem. . 74, No. 1, 2002, pp. 85-91.

[7] Graham L. Simpson, Timothy P. Heffron, Estíbaliz Merino, and Timothy F. Jamison: Ladder Polyether Synthesis via Epoxide-Opening Cascades Using a Disappearing Directing Group . (Communication) In: J. Am. Chem. Soc. . 128, No. 4, 2006, pp. 1056-1057. doi : 10.1021 / ja057973p .