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Heterogeneous Catalysis
Giovanni Sartori,*
,
Roberto Ballini,
Franca Bigi,
Giovanna Bosica,
Raimondo Maggi,
Clean Synthetic Methodologies Group, Dipartimento di Chimica Organica e Industriale dellUniversita` , Parco Area delle Scienze 17A,
43100 Parma, Italy, Dipartimento di Scienze Chimiche dellUniversita` , Via S. Agostino 1, 62032 Camerino (MC), Italy, and
Dipartimento di Chimica Organica A. Mangini dellUniversita` , V.le Risorgimento 4, 40136 Bologna, Italy
Received June 11, 2003
Contents
1. Introduction 199
2. Hydroxy Protecting Groups 203
2.1. Esters 204
2.1.1. Protection 204
2.1.2. Deprotection 206
2.2. Silyl Ethers 207
2.2.1. Protection 207
2.2.2. Deprotection 208
2.3. Alkoxyalkyl Ethers 209
2.3.1. Protection as THP Ethers 209
2.3.2. Protection as Other Alkoxyalkyl Ethers 212
2.3.3. Deprotection 212
2.4. Tosylates 214
2.5. Selective Protection of Polyfunctional
Compounds
215
2.6. Selective Deprotection of Polyprotected
Compounds
217
2.7. Redox Deprotections 221
3. Thiol Protecting Groups 223
4. Carboxy Protecting Groups 223
4.1. Protection 224
4.2. Deprotection 226
5. Carbonyl Protecting Groups 227
5.1. Acetals 227
5.1.1. Protection 227
5.1.2. Deprotection 231
5.2. Dithioacetals 233
5.2.1. Protection 233
5.2.2. Deprotection 235
5.3. 1,3-Oxathiolanes 237
5.4. 1,1-Diacetates (Acylals) 238
5.4.1. Protection 238
5.4.2. Deprotection 239
5.5. Nitrogenous Derivatives 240
5.5.1. Protection 240
5.5.2. Deprotection 241
6. Amino Protecting Groups 242
6.1. Protection 242
6.2. Deprotection 244
7. Concluding Remarks 246
8. Acknowledgments 246
9. Abbreviations 246
10. References 246
1. Introduction
Fi ne chemi cal s are compl ex and mul ti functi onal
mol ecul es, often characteri zed by l ow vol ati l i ty and
l i mi ted thermal stabi l i ty, whose manufacture gener-
al l y i s based on mul ti step synthesi s performed i n the
l i qui d phase and frequentl y i nvol vi ng protecti on-
deprotecti on steps. The use of bl ocki ng functi ons i n
organi c synthesi s, devel oped for nearl y 100 years,
makes more compl ex the enti re syntheti c pl an si nce
i t requi res at l east two addi ti onal steps. At the same
ti me, envi ronmental and economi c consi derati ons
have created i nterest, i n both academi c and i ndus-
tri al research, i n desi gni ng syntheti c procedures that
are cl ean, sel ecti ve, hi gh-yi el di ng, and mani pul a-
ti vel y easy.
I n fact, as cl earl y recogni zed by Shel don, ...tradi -
ti onal concepts of process effi ci ency are changi ng
from an excl usi ve focus on chemi cal yi el d to one that
assi gns economi c val ue to el i mi nati ng waste....
1
An extensi ve appl i cati on of heterogeneous catal ysi s
i n syntheti c chemi stry can hel p to achi eve new
sel ecti ve reacti ons, to l ower the waste producti on,
and, fi nal l y, to render more attracti ve the syntheti c
process from both the envi ronmental and al so the
economi c poi nt of vi ew, i n agreement wi th some
parameters of the i deal synthesi s recentl y pre-
sented by Wender.
2
I ndeed, sol i d catal ysts can be easi l y separated from
the reacti on products by si mpl e fi l trati on and quan-
ti tati vel y recovered i n the acti ve form. They can be
recycl ed, maki ng l ess expensi ve the preparati on of
sophi sti cated fi ne chemi cal s and, at the same ti me,
avoi di ng contami nati on of the products by trace
amounts of metal s.
The heterogeneous catal ysi s that was ori gi nal l y
studi ed and appl i ed i n bul k chemi stry wi th parti cul ar
i nterest to petrochemi cal i ndustry was more recentl y
extended to syntheti c organi c chemi stry for produc-
ti on of fi ne chemi cal s and pharmaceuti cal s.
3
Among
the fi rst reacti ons performed under heterogeneous
catal ysi s are the hydrogenati ons and, i n general , the
redox processes whi ch are extensi vel y appl i ed i n
syntheti c organi c chemi stry. Aci d-base heteroge-
* To whom correspondence shoul d be addressed. Phone: +39 0521
905551. Fax: +39 0521 905472. E-mai l : gi ovanni .sartori @uni pr.i t.
Di parti mento di Sci enze Chi mi che del l Uni versi ta`.