Italian chemists' contributions to named reactions in organic synthesis: an historical perspective

Abstract

From the second half of the 19th century up to modern times, the tremendous contribution of Italian chemists to the development of science resulted in the discovery of a number of innovative chemical transformations. These reactions were subsequently christened according to their inventors' name and so entered into the organic chemistry portfolio of "named organic reactions". As these discoveries were being conceived, massive social, political and geographical changes in these chemists' homeland were also occurring. In this review, a brief survey of known (and some lesser known) named organic reactions discovered by Italian chemists, along with their historical contextualization, is presented.

Scheme 1

The Piria diazotization reaction (1846).

Scheme 2

The Piria aminosulfonic acid synthesis (1851).

Scheme 3

“Bertagnini’s salt” (1851).

Scheme 4

The Bertagnini reaction (1856) later modified by Perkin (1868).

Scheme 5

The Cannizzaro reaction (1853).

Figure 1

Maps of Italy in 1859 (A), 1860 (B) and 1861 (C).

Figure 2

The founding act of the Gazzetta Chimica Italiana (Italian Chemical Gazette) (29 September 1870, A) and the frontispiece of its first issue (31 March 1871, B).

Scheme 6

The Schiff base synthesis (1864).

Scheme 7

The Ciamician-Dennstedt rearrangement (1881).

Figure 3

The dawn of photochemistry. Ciamician surrounded by a number of sun-exposed flasks on his laboratory terrace at the University of Bologna.

Scheme 8

The Ciamician photocoupling (1900).

Scheme 9

The Plancher rearrangement (1898).

Scheme 10

The Biginelli pyrimidine synthesis (1891).

Scheme 11

The Guareschi reaction (1896).

Scheme 12

The Ponzio reaction (1897).

Scheme 13

The Pellizzari reaction (1894).

Scheme 14

The Ortoleva-King reaction (1900).

Scheme 15

The Betti reaction (1900).

Figure 4

The negative impact of war on scientific publications. Note the smaller size of the Gazzetta Chimica Italiana volumes between 1916 and 1919 (top) and between 1942 and 1945 (bottom) (from the Nerviano Medical Sciences library).

Scheme 16

The Angeli-Rimini reaction (1901).

Scheme 17

The Bargellini reaction (1906).

Scheme 18

The Paternò-Büchi [2 + 2] cycloaddition (1909).

Scheme 19

The Gastaldi pyrazine synthesis (1921).

Scheme 20

The Passerini reaction (1921).

Scheme 21

The Amadori rearrangement (1925).

Scheme 22

The Mascarelli fluorene synthesis (1936).

Scheme 23

The Ziegler-Natta isotactic polypropylene synthesis (1955).

Scheme 24

The Berti Olefination (1954).

Scheme 25

The Caglioti reduction (1964).

Scheme 26

The Minisci reaction (1971).

Scheme 27

The Piancatelli rearrangement (1976).

Scheme 28

The Lombardo olefination (1982).

Scheme 29

The Still-Gennari reaction (1983).

Scheme 30

The Kagan-Modena reaction (1984).

Scheme 31

The Guarna-Brandi reaction (1986).

Scheme 32

The Dondoni homologation reaction (1986).

Scheme 33

The Rosini-Bartoli reductive nitroarene alkylation (1978).

Scheme 34

The Bartoli indole synthesis (1989).

Scheme 35

The Cacchi reaction (1992).

Scheme 36

The Prato reaction (1993).

Scheme 37

The Catellani reaction (1997).

Figure 5

The first page of the last article published in the Gazzetta Chimica Italiana (1997, 127, 837–842) (from the Nerviano Medical Sciences library).