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Olefin Selectivities in the Addition of Carbenes.

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We have found that the radical addition of PH functionalized mono- and bisphosphanes to allylphosphanes offers, in principle, a more variable synthetic method, and
demonstrate its efficiency by means of the one-step preparation of the two chiral ligands 1 and 2, as well as of the
derivative 3 (2 h at 110 “C in presence of 2,2’-azobis(isobutyronitrile) having permethylated terminal phosphino
groups141.
After column chromatography, 1, 2 , and 3 were obtained in yields of ca. 50% as colorless oils, which were
characterized by their N M R data (Table 1).
The diastereotopicity of the Me2P fragments is clearly
evident in the ’H-NMR spectra of 1 and 3: in each compound the methyl protons display two doublets with a
chemical shift difference of 0.02 ppm. In 2, in contrast, the
nonequivalence of the methyl protons cannot be detected,
even at 270 MHz.
Since the synthetic building blocks required for the
phosphane/allylphosphane coupling are readily obtainable, we expect that using this method a series of systematically variable ligands can be prepared, by means of
which the reactivity of transition-metal complexes can be
controlled.
where E is proportional to the logarithm of the rate constant and d E corresponds to its (differential) change. From
relationship (a), changes in the reactivity of a carbene (i. e.
its selectivity), therefore result additively and linearly from
changes in the individual quantities (e.9. orbital energies,
frontier orbital coefficients, etc.).
With respect to (a) the following correlations were investigated: ( I ) n-ionization potentials of the olefins and the
logarithms of the relative rate constants in addition reactions with CClz [IgkreI=a.E,(olefin)+c] over as large a
range of reactivity as possible141(krel= 1 to 1000; cf. Fig. 1);
(2) ditto for all the carbenes studied under standard conditionsI6], not only with (case a) but also without (case b)
consideration of the different coefficients of the HOMO’S
of the various olefins [for case a) Ink,,,=a. E,(olefin)+
b . coeff(o1efin) + c holds] (see Table 1). The coefficients
were calculated using the CNDO/2 method.
&.o t
t
Received: November 2, 1979;
revised: October 22, 1982 [Z 404 IE]
German version: Angew. Chem. 94 (1982) 929
The complete manuscript of this communication appears in:
Angew. Chem. Suppl. 1982. 1950-1955
[2] R. Uriarte, T. J. Mazanec, K. D. Tau, D. W. Meek, Inorg. Chem. 19(1980)
79.
[3] E. Arpac, L. Dahlenburg, Z . Nafuforsch. B 35 (1980) 146.
[4] Note added in drafting the complete manuscript: Stelzer er al. have also
oligophosphanes (inter alia. 3)
synthesized a series of methylated ‘*pL-C3”
by PH/allyl-addition: M. Baacke, 0. Stelzer, V. Wray, Chem. Ber. 113
(1980) 1356; M. Baacke, S. Hietkamp, S. Morton, 0. Stelzer, ibid. 114
(1981) 2568.
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---+
Olefin Selectivities in the Addition of Carbenes**
Fig. I. Correlation of the logarithm of the relative rate constants with the x .
ionization potentials of substituted olefins for the IJaddition of CCIz.
By Wolfgang W. Schoeller*, Nevzat Aktekin, and
Henniger Friege
At variance with previous conceptions1’], according to
the differential frontier model singlet carbenes can be divided into two classes depending on whether they follow a
direct or inverse reactivity-selectivity relationshipI2]. We
have now experimentally tested this model for the electrophilic carbene series and placed it on a quantitative basis.
The following relationship applies to a change in reactivity of a carbene (C) with an olefin (0):
As shown in Fig. 1, the relative reactivity of CC12 clearly
increases as the x-ionization potential of the olefin decreases, however, a linear relationship is impaired by the
large scattering of the points. On the other hand the correlations are greatly improved (r2= 0.90, case 2a) for the car-
Table I . Parameters for the linear equation from method (2a) and relative selectivities of the carbenes (S=a/a,,,J calculated from it.
[*I Priv.-Doz. Dr. W. W. Schoeller, Dr. N. Aktekin
Fakultat fur Chemie der Universitat
Postfach 8640, D-4800 Bielefeld 1 (Germany)
Dr. H. Friege
Organisch-chemisches lnstitut der Universitat
Orleans-Ring 23, D-4400 Miinster (Germany)
I**] This work was supported by the Deutsche Forschungsgemeinschaft and
Carbene
a
b
rz
S
Shoosq
[61
C F2
CCI*
CBr2
CF’H
CFCl
CClMe
CBrCOIEt
CClSMe
CFPh
CClPh
CBrPh
CClcPr
- 8.75
36.63
24.96
15.80
-0.12
30.88
10.08
7.01
24.28
22.87
20.96
16.74
9.84
0.933
0.927
0.887
0.945
0.918
0.872
0.923
0.961
0.904
0.850
0.838
0.852
1.51
1.00
0.64
0.13
1.28
0.49
0.29
0.95
0.88
0.81
0.67
0.40
1.48
1.00
0.65
0.12
1.28
0.50
0.29
0.93
0.89
0.83
0.70
0.41
- 5.80
-3.70
- 0.74
-7.41
-2.82
- 1.66
-5.51
- 5.09
-4.61
- 3.88
- 2.30
the Fonds der chemischen Industrie.
932
0 Verlag Chemie GmbH. 6940 Weinheim, I982
0570-0833/82/1212-0932 $ 02.50/0
Angew. Chem. Int. Ed. Engl. 21 (1982) No. 12
9.8
benes investigated under standard conditions, if in the parameter equation the different coefficients of the HOMO's
at the various oletins are taken into consideration (Table
1).
The parameters a of the linear equations (Table 1) are a
quantitative measure of the change in reactivity of a carbene with the n-ionization potential of the olefin. For CC12
a relative selectivity scale is obtained, which is consistent
with that reported by Moss et aLL6].According to differential frontier orbital theory, it is therefore possible to predict
the relative reactivity of a carbene with an olefin from the
corresponding linear equations. This only requires know-
ledge of the n-ionization potential of the olefin and the orbital coefficients of its HOMO's.
Received: February 17, 1982 [Z 405 IE]
German version: Angew. Chem. 94 (1982) 930
The complete version of this communication appears in:
Angew. Chem. Suppl. 1982, 1992-2003
[I] P. S. Skell, M. Cholod, J. Am. Chem. Soc. 91 (1969) 7131.
[2] W. W. Schoeller, Angew. Chem. 93 (1981) 685; Angew. Chem. I n ( . Ed.
Engl. 20 (1981) 698.
[4] E. Dehmlow, A. Eulenberger, Angew. Chem. 90 (1978) 716; Angew. Chem.
I n [ . Ed. Engl 17 (1978) 674.
[6] R. A. Moss, C. €3. Mallon, C. T. Ho, J . A m , Chem. SOC.99 (1977) 4105;
and literature cited therein.
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