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Pd (II)-catalysed C-H fonctionnalisation of alkenes
Emilie Thiery, Jean Le Bras, Jacques Muzart
To cite this version:
Emilie Thiery, Jean Le Bras, Jacques Muzart. Pd (II)-catalysed C-H fonctionnalisation of alkenes.
12th Sigma-Aldrich Organic Synthesis Meeting, Dec 2008, Spa, Belgium. �hal-01822752�
Pd II -CATALYSED C-H FUNCTIONNALISATION OF ALKENES
Emilie THIERY,
(a)(b)Jean LE BRAS,
(b)Jacques MUZART
(b)(a)Laboratoire de Chimie Bioorganique, Département de Chimie, Facultés Universitaires Notre-Dame de la Paix,
Rue de Bruxelles, 61 B-5000 Namur BELGIQUE (b) Institut de Chimie Moléculaire de Reims, CNRS UMR 6229, Université de Reims Champagne Ardenne, UFR des Sciences exactes et naturelles, BP 1039, 51687 REIMS Cedex 2 FRANCE
emilie.thiery@fundp.ac.be
C-H BONDS FUNCTIONNALISATION: COMPETITION BETWEEN VARIOUS COUPLINGS
ET411
100 120 140 160 180 200 220 240 260 280 300 320 340 360 380 400 420 440 460 480 500 520
0 m/z 100
%
EX2313 173 (5.567) Cm (131:259) 1: TOF MS ES+
5.01e3
211.0
210.0
209.0
186.3
105.1 102.1
178.0
204.0
213.0
252.0
251.0
215.0
250.0
242.1 231.0
254.0
291.0 290.0 256.0
271.1
270.1
273.1 289.0
275.1
288.0
293.0
295.0
332.1 331.1 310.0 329.1
351.2
475.2 453.2
371.1 416.2 433.1 457.1 479.2
510.2
O Pd
H+ O
O Pd+
187 [CA-2L-X]+
[CB-L+H]+
[CB+H]+ [CB-2L+H]+
L = MeCN X = CF3CO2-
351
[CD-2L-C5H5O]+
[CD-L-C5H5O]+
[CG-2L-H]+
[CGf-L-H]+
[CGf-H]+ O
Pd+
371
O Pd+
O
412 453
332 271
310 291
ALLYLIC OXIDATION C-C BOND
FORMATION
Parameters having an influence on the selectivity
SYNTHESIS OF DIFURYLALKANES: MECHANISM STUDY WITH STYRENE
ESI (+)-MS analysis of the reaction mixture
Pd(OCOCF3)2, BQ
MeCN, AcOH, 20°C, 15 min O
+
Proposed Mechanism Coupling between 2-methylfuran and styrene-d
8: deuterium migration
Competition
E. Thiery, D. Harakat, J. Le Bras, J. Muzart, Organometallics. 2008, 27, 3996-4004.
20 Examples
1. I. I. Moiseev, M. N. Vargaftik, Coord. Chem. Rev. 2004, 248, 2381-2391.
2. E. M. Beccalli, G. Broggini, M. Martinelli, S. Sottocornola, Chem. Rev. 2007, 107, 5318-5365.
3. Palladium catalyzed C-H bonds fonctionnalization in “Green Chemistry Research Trends”, J. Le Bras, E. Thiery, NOVA SCIENCE Publishers, Inc. 2008, in press.
Palladium Co-solvent
Coupling between 2-methylfuran and styrene
Ph
O Ph O
O
O Ph +
O
50/50
100 % 100 %
Low coordinating solvent
or without co-solvent Pd(OAc)2
Pd(OCOCF3)2 MeCN
Acknowledgment: The city of Reims for a Ph.D.
studentship to E.T. and the CNRS for financial support through the program “Chimie et
Développement Durables”.
L2PdX2
X = OAc, OCOCF3 O
XPd O
O
Ph O XPd
Pd O O
CB CC
L2
L2 L2
L
L HX
C-H activation
insertion Ph
XPd O L
Ph
L
XPd O L
O
C-H activation L
complexation
HX
To a oxidative Heck coupling
To the difurylalkanes formation
O
O
O
O +
85:15, 60 % O
+
Pd(OCOCF3)2 (0.05 equiv.) BQ (2 equiv.)
AcOH/MeCN (1:6), 20°C, 20h 5 equiv.
L2PdX2
XPd O
Pd O O
CA
CB
CD1 O Ph
O Pd
CE1 O Ph
O Pd
H CG1
O Ph
PdH
O
PdL2 BQ + 2HX
HQ
L2
L2
L2 L2
HX
HX
X = CF3COO- L = MeCN
C-H activation
C-H activation
insertion
ββββ-H-elimination insertion
oxidation
O
O
Ph reductive elimination
O Ph
O
H H
Pd(OCOCF3)2, BQ O
O
O CD2
O D O
D D D5
D D
D5 D + D5
MeCN, AcOH, 20°C, 72 h
conv = 100 %, yield = 66 %
D +
Pd(OCOCF3)2 (0.05 equiv.) BQ (2 equiv.)
MeCN/AcOH (6:1), r.t., 20 h
O O O
O
Pd(OAc)2 (0.05 equiv.), BQ (2 equiv.)
O (5 équiv.)
MeCN/AcOH (1:1), 40°C, 24 h
85:15, 94 %
OAc E/Z = 19:1, 52 % Pd(OAc)2 (0.05 equiv.), BQ (2 equiv.)
CH2Cl2/AcOH (1:1), 40°C, 24 h O (1.1 équiv.)
O
E, 20 %
