G. Brunner, S. Elmer, F. Schröder
FULL PAPER
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Mueller, EP908455, priority 9.19.1997 to Givaudan Roure
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The reactivity order of dihalomethanes is in accordance with
that of the radical halogen abstraction from these compounds.
See, for example: a) L. H. Menapace, H. G. Kuivila, J. Am.
Chem. Soc. 1964, 86, 3047–3051; b) E. M. Kosower, I.
Schwager, J. Am. Chem. Soc. 1964, 86, 5528–5535.
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J. A. Bajgrowicz, G. Frater, EP801049, priority 29.3.1997 to Gi-
vaudan-Roure (International) S. A., 1997 [Chem. Abstr. 1997,
127, 358652].
a) G. Brunner, L. Eberhard, J. Oetiker, F. Schröder, J. Org.
Chem. 2008, 73, 7543–7554; b) G. Brunner, L. Eberhard, J. Oe-
tiker, F. Schröder, Synthesis 2009, 3708–3718.
Proximal alkenes are closer to and distal alkenes further from
the heteroatom-containing functional group of a diene. See, for
example K. M. George, Y. Yuan, D. R. Sherman, C. E.
Barry 3rd, J. Biol. Chem. 1995, 270, 27292–27298.
Zinc is generally regarded as more eco-friendly than aluminum.
Release or dumping of zinc wastes, however, can be problem-
atic in some countries due to legislation constraints.
The reagent is much less pyrophoric than trialkylaluminum
reagents with lower molecular weight such as trimethylalumi-
num.
On a 50–200 g scale the reaction mass ejected through the con-
densor.
TFA: a) A. B. Charette, A. Beauchemin, S. Francoeur, J. Am.
Chem. Soc. 2001, 123, 8139–8140; b) Z. Yang, J. C. Lorenz, Y.
Shi, Tetrahedron Lett. 1998, 39, 8621–8624.
a) E. Nakamura, A. Hirai, M. Nakamura, J. Am. Chem. Soc.
1998, 120, 5844–5845; b) A. B. Charette, C. Molinaro, C. Bro-
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2341–2350.
If heated to 90 °C, uncontrollable exothermic decomposition
occured also in the presence of FeCl3. Advantageously, at 10–
25 °C the reaction temperature is sufficiently far enough from
that critical temperature region.
This addition mode allows excess carbenoid R2AlCH2Br to be
destroyed by FeCl3.
Similar exothermic effects linked to the addition mode are
known from other acid-catalyzed reactions, e.g. the acetaliza-
tion of alcohols with enolates.
Most other metallocenes were inactive: CpFe(CO)2Br,
Cp2ZrCl2, Cp2Ni, Cp2Fe (no effect), Cp2Ru (slow decomposi-
tion). Carbonylmetal compounds such as Fe(CO)5 and
Mo(CO)6 catalyzed the cyclopropanation at 25 °C, but with
sudden exothermic peaks; Fe2(CO)9, Fe powder, or Fe(acac)3
were inactive.
Reduction of (electron-poor) terminal double bonds with AlR3
in analogy to the one of carbonyl compounds. See also R–
CH2–CH2–Al + RЈ–CH=CH2 p R–CH=CH2 + RЈ–CH2–
CH2–Al, in K. Ziegler, Organometallic Chemistry (Ed.: Z.
Zeiss), Reinhold Publishing Corporation, New York, 1960, pp.
194–269 and 226.
Cyclopropanation of 1i or 1j under Simmons–Smith conditions
is similarly incomplete; see, for example: A. Goeke, EP1269982,
priority 30.6.2001 to Givaudan SA, Switzerland, 2001 [Chem.
Abstr. 2003, 138, 61094].
Preparation of substrates 1 according to the literature: 1a:
ref.[6]; 1b: R. E. Naipawer, M. Rohr, R. H. Potter, EP116903,
Givaudan, L. & Cie S. A., Switzerland, 1983 [Chem. Abstr.
1985, 102, 6870]; 1f: W. Rojahn, W. W. Bruhn, Dragoco Rep.
(Ger. Ed.) 1978, 25, 248–253; 1g: H. Kise, T. Sato, T. Yasuoka,
M. Seno, T. Asahara, J. Org. Chem. 1979, 44, 4454–4456 and
references cited therein; 1m: G. Frater, D. Helmlinger, U.
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[24]
K. H. Schulte-Elte, B. Mueller, H. Pamingle, EP155591, Fir-
menich SA, 1984 [Chem. Abstr. 1986, 105, 191435].
Replacement of TIBA by triethyl- or trioctylaluminum under
these conditions gave even higher proportions of the addition
products.
R. E. Naipawer, W. M. Easter, US4052341, Givaudan Corp.,
1976 [Chem. Abstr. 1978, 88, 22229].
K. Siirde, T. Valimae, T. Pehk, A. Erm, H. Rang, K. Leets,
Zh. Org. Khim. 1979, 15, 2028–2034 [Chem. Abstr. 1980, 92,
129086].
a) K. Maruoka, Y. Fukutani, H. Yamamoto, J. Org. Chem.
1985, 50, 4412–4414; b) K. Maruoka, S. Sakane, H. Yamam-
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[26]
[6]
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[8]
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[29]
Also higher carbenoids (iBu)3–xAl(CH2Br)x can be formed
from Al(iBu)3 and excess CH2Br2.
“Decomposition was observed when a Lewis acid (Et2AlI for
example) was added to the mixed carbenoid (iBu2AlCH2I)”;
see footnote 11 in ref.[31]
S. Miyano, H. Hashimoto, Bull. Chem. Soc. Jpn. 1973, 46, 892–
897.
A. B. Charette, A. Beauchemin, J. Organomet. Chem. 2001,
617–618, 702–708.
Electrospray Ionization Tandem Mass Spectrometry: http://
www.chen.ethz.ch/rsrch/esi/indesx.html.
R. S. Schneider, I.-P. Lorenz, H. Nöth, W. Z. Ponikwar, Z.
Anorg. Allg. Chem. 2001, 627, 1775–1781 and references cited
therein.
N. S. Zefirov, Chem. Rev. 1982, 82, 615–624.
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[9]
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[32]
[33]
[10]
[11]
[12]
[34]
[35]
[13]
[14]
[36]
Ethyl ether 1p was chosen as O-protected substrate, because
the benzyl or allyl ether of 1a were both cleaved under these
conditions (cat. FeCl3 and TIBA in CH2Br2).
[37]
[38]
In analogy to: S. C. Goel, S. K. Mehrotra, R. C. Mehrotra,
Synth. React. Inorg. Met.-Org. Chem. 1977, 7, 519–530.
A. P. S. Narula, E. M. Arruda, F. Schiet, US7172994, priority
9.12.2005 to IFF, USA, 2005 [Chem. Abstr. 2007, 146, 208394].
This patent describes the cyclopropanation of myrcenol (1h)
with excess TIBA in an excess of dichloromethane. In our
hands attempted reproduction of 3h according to Example A
of this patent gave reduction product tetrahydromyrcenol (CAS
18479-57-7), claimed product 3h was not detected by NMR
and GC/MS.
K. Ziegler, US2892858, 1959 [Chem. Abstr. 1959, 53, 99466].
A mixture of CH2Br2 and 25% NaOH was stable up to 85 °C.
2-Methylpropane, recovered by this method, is relatively pure
according to NMR spectroscopy. Impurities: CH2Br2 (1%),
iBuBr (0.1%), MeBr (0.1%).
Azeotropes: CH2Br2/2-propanol (60:40, 87 °C), CH2Br2/2-pro-
panol (66:33, 95 °C): J. Gmehling, J. Menke, K. Fischer, J.
Krafczyk, Azeotropic Data, VCH Verlagsgesellschaft,
Weinheim, New York, Basel, Cambridge, Tokyo, 1994.
The close boiling points of iBuBr (b.p. 92 °C) and CH2Br2 (b.p.
97 °C) necessitate good distillation columns with enough theo-
retical plates.
NL6401153, Firmenich, 1964 [Chem. Abstr. 1965, 62, 15429].
L. Turin, GB2383327, priority 20.8.2002 to Flexitral Inc., 2002
[Chem. Abstr. 2003, 139, 53170]. Attempted reproduction of
the procedure described in this patent gave acitral (14) with
only 37% yield and 76% purity after flash chromatography.
The excess of halogenated solvent used in this procedure is an-
other problem.
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