Details
| Original language | English |
|---|---|
| Pages (from-to) | 177-190 |
| Number of pages | 14 |
| Journal | Synlett |
| Issue number | 2 |
| Publication status | Published - 24 Jan 2007 |
Abstract
This account shows that a silyl-substituted carbanion may be looked upon as a latent dianion which, in the reaction with biselectrophiles, yields ring-closure products. The biselectrophile is normally an epoxide carrying a remote leaving group. The carbanion will open the epoxide and allow for a C→O silyl shift thus generating the new carbanion. This then reacts with the second functional group of the biselectrophile. The flexibility of the approach is demonstrated by using various acceptor groups on the initial carbanion 1 (SR, SiR3, CN) while the range of biselectrophiles includes epoxyalkyl tosylates, bisepoxides, epoxy-aziridines, vinylepoxides, and, for heterocyclic synthesis, bromoalkyl isocyanates. Instead of the epoxide, an ester group may act as electrophile. 1 Introduction 2 Cyclopropanes by Homo-Peterson Reaction 3 Epoxyalkyl Tosylates as Biselectrophiles 3.1 Synthesis of Cyclobutanols 3.2 Synthesis of Cyclopentanols 3.3 Larger Carbocyclic Rings 4 Bisepoxides as Biselectrophiles 5 Vinylepoxides as Biselectrophiles 6 Phthalates as Biselectrophiles 7 Bromoalkyl Isocyanates as Biselectrophiles 8 Divertimento! 9 Conclusion.
Keywords
- Cycloalkanes, Domino reaction, Rearrangement, Ring closure, Silicon
ASJC Scopus subject areas
- Chemistry(all)
- Organic Chemistry
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In: Synlett, No. 2, 24.01.2007, p. 177-190.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Domino synthesis of carbo- and heterocycles involving a 1,3 or 1,4 C→O silyl migration
AU - Schaumann, Ernst
AU - Kirschning, Andreas
PY - 2007/1/24
Y1 - 2007/1/24
N2 - This account shows that a silyl-substituted carbanion may be looked upon as a latent dianion which, in the reaction with biselectrophiles, yields ring-closure products. The biselectrophile is normally an epoxide carrying a remote leaving group. The carbanion will open the epoxide and allow for a C→O silyl shift thus generating the new carbanion. This then reacts with the second functional group of the biselectrophile. The flexibility of the approach is demonstrated by using various acceptor groups on the initial carbanion 1 (SR, SiR3, CN) while the range of biselectrophiles includes epoxyalkyl tosylates, bisepoxides, epoxy-aziridines, vinylepoxides, and, for heterocyclic synthesis, bromoalkyl isocyanates. Instead of the epoxide, an ester group may act as electrophile. 1 Introduction 2 Cyclopropanes by Homo-Peterson Reaction 3 Epoxyalkyl Tosylates as Biselectrophiles 3.1 Synthesis of Cyclobutanols 3.2 Synthesis of Cyclopentanols 3.3 Larger Carbocyclic Rings 4 Bisepoxides as Biselectrophiles 5 Vinylepoxides as Biselectrophiles 6 Phthalates as Biselectrophiles 7 Bromoalkyl Isocyanates as Biselectrophiles 8 Divertimento! 9 Conclusion.
AB - This account shows that a silyl-substituted carbanion may be looked upon as a latent dianion which, in the reaction with biselectrophiles, yields ring-closure products. The biselectrophile is normally an epoxide carrying a remote leaving group. The carbanion will open the epoxide and allow for a C→O silyl shift thus generating the new carbanion. This then reacts with the second functional group of the biselectrophile. The flexibility of the approach is demonstrated by using various acceptor groups on the initial carbanion 1 (SR, SiR3, CN) while the range of biselectrophiles includes epoxyalkyl tosylates, bisepoxides, epoxy-aziridines, vinylepoxides, and, for heterocyclic synthesis, bromoalkyl isocyanates. Instead of the epoxide, an ester group may act as electrophile. 1 Introduction 2 Cyclopropanes by Homo-Peterson Reaction 3 Epoxyalkyl Tosylates as Biselectrophiles 3.1 Synthesis of Cyclobutanols 3.2 Synthesis of Cyclopentanols 3.3 Larger Carbocyclic Rings 4 Bisepoxides as Biselectrophiles 5 Vinylepoxides as Biselectrophiles 6 Phthalates as Biselectrophiles 7 Bromoalkyl Isocyanates as Biselectrophiles 8 Divertimento! 9 Conclusion.
KW - Cycloalkanes
KW - Domino reaction
KW - Rearrangement
KW - Ring closure
KW - Silicon
UR - http://www.scopus.com/inward/record.url?scp=33847038785&partnerID=8YFLogxK
U2 - 10.1055/s-2007-968023
DO - 10.1055/s-2007-968023
M3 - Article
AN - SCOPUS:33847038785
SP - 177
EP - 190
JO - Synlett
JF - Synlett
SN - 0936-5214
IS - 2
ER -