Angewandte Chemie International Edition
10.1002/anie.201800128
COMMUNICATION
The ferrocene-backboned diamine 3 shows an exciting
reactivity towards tBuLi (Scheme 2).
bond cleavage (thermodynamic control), extending the very few
numbers of known such C-C bond scissions reported in the
literature.[18] However, at −100 °C (kinetic control) metalation of
the Cp-3 position is observed. These results are motivation to
continue extensive studies including DFT calculations of this class
of compounds, for instance in the direction related to
enantioselective syntheses of ferrocene-backboned ligands for the
design of transition metal-based catalysts.
thermodynamic control
kinetic control
a
−
3
tBuLi, SiMe Cl
−
−
)
tBuH, LiCl,
iPr
Me
2
C=CH
2
iPr
NH
iPr
b) tBuLi, H
2
O
E
−
−
−
tBuH, LiOH,
Me
C=CH
tBuLi, SnCl2
N
NMe
2
NMe
2
NH
*
NMe
2
iPr
2
2
iPr
iPr
c
*
−)
−
H
tBu
tBu
H
−
tBuH, LiCl,
H
tBuLi, SiMe
−
−
3
Cl
H
Me
2
C=CH
2
tBuH, LiCl
SiMe
3
Fe
Fe
Et O
100°C, 10 h
Fe
Et
2
O
−
2
2
5 °C, 24 h
9
9
9
a, E = SiMe
b, E = H
3
3
10
Experimental Section
c, E = SnCl
9c
For the synthesis and complete characterization of the compounds 1-10, see the
Electronic Supporting Information. CCDC-1580427 (1), CCDC-1580428 (2),
CCDC-1580429 (3), CCDC-1580430 (4), CCDC-1580431 (5), CCDC-1580432
(7), CCDC-1580433 (8), CCDC-1580434 (9c), and CCDC-1580435 (10) contain
the supplementary crystallographic data for this paper. Copies of the data can be
obtained free of charge on application to the Cambridge Crystallographic Data
Centre, 12 Union Road, Cambridge CB2 1EZ, UK (fax: (+44)1223-336-033; e-
mail: deposit@ccdc.cam.ac.uk, http://www.ccdc.cam.ac.uk).
Keywords: Tin • germanium • lithium • ferrocene • carbon-
Scheme 2: Reactivity of ferrocene 3 towards tBuLi, yielding 9a-c and 10.
carbon bond cleavage
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Thus, treatment of 3 with tBuLi at room temperature
thermodynamic control) and subsequent addition of SiMe Cl, H
or SnCl provided the corresponding ferrocene derivatives 9a, 9b,
(
3
2
O
2
and 9c, respectively, as orange oils (9a, 9b) or deep red crystalline
[
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3
3
unprecedented C(sp )–C(sp ) bond cleavage and loss of the t-butyl
substituent was observed. Single crystals of the tin(II) derivative 9c
suitable for X-ray diffraction analysis were obtained from its diethyl
ether solution. For detailed information on 9a-c see the Supporting
Information.
1
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When performing the reaction under kinetic control at –100 °C,
lithiation of the Cp-H3 position took place. Subsequent addition of
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2
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molecular structure see Supporting Information.
The reactions presented above have been reproduced several
times. In course of the reaction performed at room temperature,
formation of a gas mixture consisting of 2-methylpropane and 2-
methylpropene was observed. So far, no mechanistic studies
including DFT calculations were carried out. Notably, the reaction
of compound 3 with lithium hydride, LiH, proceeds as expected
under metalation of the NH function without loss of the t-Bu
substituent giving exclusively the lithium amide 2.
2
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[
4]
In conclusion, the convenient and in part stereoselective
syntheses in large scale of the novel N-functionalized ferrocene
derivatives 1-5 are reported. Subsequent reactions with electrophiles
2
008, 27, 457.
[5]
[6]
[7]
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such as GeCl
2 2
∙dioxane and SnCl gave access to the first ferrocene-
backboned subvalent heteroleptic group XIV element amide
chlorides 6 and 7, respectively, holding potential as redox-active
ligands.[17] Most importantly, the diamine 3 reacts with tbutyl
lithium at room temperature under an unprecedented carbon-carbon
[8]
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6
167.
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