Selenosilanes mediated stereoselective synthesis of polyfunctionalized organic molecules

Article abstract of DOI:10.1080/10426500801900923

Bis(trimethylsilyl)selenide (HMDSS) acts as an efficient reagent in the TBAF catalyzed reaction with different substituted epoxides, episulfides, and aziridines, leading to -functionalized diselenides in a highly regio- and stereoselective way. When using

Full text of DOI:10.1080/10426500801900923

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Phosphorus, Sulfur, and Silicon
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Selenosilanes Mediated
Stereoselective Synthesis of
Polyfunctionalized Organic
Molecules
Alessandro Degl'Innocenti a , Antonella Capperucci
a , Giulio Castagnoli a , Irene Malesci a , Caterina
Tiberi a & Brunella Innocenti a
a Università di Firenze, Dipartimento di Chimica
Organica and HBL , Sesto Fiorentino, Italy
Published online: 29 Oct 2008.
To cite this article: Alessandro Degl'Innocenti , Antonella Capperucci , Giulio
Castagnoli , Irene Malesci , Caterina Tiberi & Brunella Innocenti (2008) Selenosilanes
Mediated Stereoselective Synthesis of Polyfunctionalized Organic Molecules,
Phosphorus, Sulfur, and Silicon and the Related Elements, 183:4, 966-969, DOI:
10.1080/10426500801900923
To link to this article: http://dx.doi.org/10.1080/10426500801900923
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Phosphorus, Sulfur, and Silicon, 183:966–969, 2008
Copyright © Taylor & Francis Group, LLC
ISSN: 1042-6507 print / 1563-5325 online
DOI: 10.1080/10426500801900923
Selenosilanes Mediated Stereoselective Synthesis
of Polyfunctionalized Organic Molecules
Alessandro Degl’Innocenti, Antonella Capperucci,
Giulio Castagnoli, Irene Malesci, Caterina Tiberi,
and Brunella Innocenti
Universita` di Firenze, Dipartimento di Chimica Organica and HBL,
Sesto Fiorentino, Italy
Bis(trimethylsilyl)selenide (HMDSS) acts as an efficient reagent in the TBAF cat-
alyzed reaction with different substituted epoxides, episulfides, and aziridines,
leading to β-functionalized diselenides in a highly regio- and stereoselective way.
When using α-bromo alkyl ethers as trapping agent, 1,3-oxaselenolanes and 1,3-
thiaselenolanes can be isolated, while 1,3-selenazolidines could be obtained through
reduction of β-amino diselenides followed by in situ treatment with different alde-
hydes.
Keywords Silyl-selenide; epoxides; episulfides; aziridines; selenoheterocycles
INTRODUCTION
The chemistry of organoselenium compounds is of great interest both
from the synthetic and biologic point of view.1 Selenated reagents are
in fact used either as useful intermediates in the synthesis of hete-
rocyclic compounds2 or in the synthesis of selenium containing cyclic
structures.3 Although a number of synthetic processes based on sele-
nium chemistry have been reported along the years, little is known
about methodologies based on the reactivity of selenosilanes.
Our long dated interest in the chemical behavior of
bis(trimethylsilyl)sulfide (HMDST), led us to elucidate its efficiency
as a useful reagent in the delivery of sulfur functionalities, such as
the generation of a variety of thiocarbonyl compounds.4 More recently
we reported the TBAF catalyzed reaction of a range of substituted
epoxides with HMDST, that smoothly afforded a direct and simple
Address correspondence to Alessandro Degl’Innocenti, Universita` di Firenze, Dipar-
timento di Chimica Organica and HBL, Via della Lastruccia 13, 50019 Sesto Fiorentino,
Italy. E-mail: alessandro.deglinnocenti@unifi.it
966

Synthesis of Polyfunctionalized Organic Molecules
967
access to β-mercaptoalcohols in a highly regio- and stereoselective
way.5
On the other hand, the chemistry of the corresponding selenium
derivative, bis(trimethylsilyl)selenide (HMDSS, TMS-Se-TMS)6 has re-
ceived much less attention, despite the relevance that organoselenium
compounds have actually gained. To the best of our knowledge, only
few reports dealing with the reactivity of silyl selenides with hetero-
cyclic rings have been reported. In particular, reactions of phenylse-
leno(trimethylsilane) towards tetrahydrofurans7 and epoxides,8 under
Lewis acid (ZnI2) or basic conditions (n-BuLi) were described. Lewis
acid catalyzed reaction of epoxides with the related PhSeSnBu3 has
also been reported.9 On the contrary, a large number of papers con-
cerning the reactivity of diselenides and different selenium anions with
epoxides have been described in the literature.10
RESULTS AND DISCUSSION
In this letter we want to report on our recent findings on the reactivity
of hexamethyldisilaselenane (HMDSS) 1 with epoxides 2 that affords a
highly regioselective ring opening of these small membered heterocyclic
rings under TBAF catalysis (Scheme 1).
SCHEME 1
Several attempts to isolate the β-hydroxy silyl selenide (or selenol)
intermediates were unsuccessful, and the corresponding β-hydroxy dis-
elenides 3 were always obtained. The reaction proved quite general,
occurring with aliphatic and aromatic substituents on the epoxide.
When enantiopure oxiranes are reacted, optically active β-hydroxy dis-
elenides were regioselectively formed. The described reactivity is not
limited to epoxides, but may be conveniently extended to other ring
strained heterocycles, such as episulfides 4 and N-tosyl-aziridines 5,
leading to a convenient access to several β-mercapto diselenides 6 and
β-amino diselenides 7, respectively (Scheme 2).
Attack generally occurs at the less hindered position to provide ring-
opening products. With the aim to gain evidence for the formation of
the transient β-functionalized silyl selenides, the reaction of three-
membered heterocycles with HMDSS was run in the presence of an

968
A. Degl’Innocenti et al.
SCHEME 2
aldehyde under TBAF catalysis, but no evidence of the formation of the
desired pentaatomic heterocycles was detected. Nevertheless, when 2-
methyloxirane 2a and 2-methylthiirane 4a were treated with HMDSS
in the presence of the more reactive 1-bromo-1-methoxyethane 8,11
the expected 1,3-oxaselenolane 9a and 1,3-thiaselenolane 10a were ob-
tained (Scheme 3), arising from the in situ trapping of the β-hydroxy
silyl selenide intermediate by the bromo derivative, with a d.r. of 94:6
and 70:30, respectively.
SCHEME 3
In these conditions, 1,3-selenazolidines were unfortunately obtained
in very poor yield (ca. 10%). Thus, taking advantage of the possible
reduction of diselenides in acidic medium by hypophosphorous acid,12
β-amino diselenides 7 were reacted with H3PO2 and in situ treated with
benzaldehyde (Scheme 4). Under these conditions, the reaction afforded
the desired 1,3-selenazolidines 11 in good yields, with the formation of
different N-tosyl-2-phenyl-4-substituted heterocycles, as a mixture of
cis and trans diastereoisomers.
SCHEME 4

Synthesis of Polyfunctionalized Organic Molecules
969
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