On the configurational stability of chiral heteroatom-substituted [D 1]Methylpalladium complexes as intermediates of stille and suzuki-miyaura cross-coupling reactions

Article abstract of DOI:10.1002/ejoc.201300439

Enantiomerically pure (S)-tributylstannyl[D₁]methanol and (R)- and (S)-tributylstannyl[D₁]methyl benzoates were Stille-coupled with bromobenzene and benzoyl chloride in 1,4-dioxane and toluene using [(Ph ₃P)₄Pd] or [(Ph₃P)₂PdCl₂] either alone or in combination with CuCN as cocatalyst at temperatures up to 80 °C. The products were found to be enantiomerically pure. (R)- and (S)-N-(tributylstannyl[D₁]methyl)phthalimides gave enantiomerically pure products with benzoyl chloride, but with bromobenzene protected phenyl[D₁]methylamines gave products of only 52-69 % ee depending on the solvent used. Tributyl(thio[D₁]methyl)stannanes could not be Stille-coupled with benzoyl chloride or with bromobenzene. Similarly, dimethyl phenyl[D₁]methylboronate underwent a Suzuki-Miyaura coupling with bromobenzene to give phenyl[D₁]methylsilane with 99 % ee. All couplings followed a retentive course and, except in one case, the intermediate [XCHDPdL_n] complexes were found to be microscopically configurationally stable. Stille coupling of enantiomerically pure tributylstannyl[D₁]methanol, its benzoate, and the N-(tributylstannyl[D₁]methyl)phthalimide with bromobenzene and benzoyl chloride furnished products containing a chiral XCHD group. Overall net retention of configuration was found in all cases.

Full text of DOI:10.1002/ejoc.201300439

FULL PAPER
DOI: 10.1002/ejoc.201300439
On the Configurational Stability of Chiral Heteroatom-Substituted
[D1]Methylpalladium Complexes as Intermediates of Stille and
Suzuki–Miyaura Cross-Coupling Reactions
Petra Malova Krizkova[a] and Friedrich Hammerschmidt*[a]
Keywords: Palladium / Isotopic labeling / Enantioselectivity / Cross-coupling / Chirality / Reaction mechanisms
Enantiomerically pure (S)-tributylstannyl[D1]methanol and
(R)- and (S)-tributylstannyl[D1]methyl benzoates were Stille-
coupled with bromobenzene and benzoyl chloride in 1,4-di-
oxane and toluene using [(Ph3P)4Pd] or [(Ph3P)2PdCl2] either
alone or in combination with CuCN as cocatalyst at tempera-
tures up to 80 °C. The products were found to be enantiomer-
ically pure. (R)- and (S)-N-(tributylstannyl[D1]methyl)phthal-
imides gave enantiomerically pure products with benzoyl
chloride, but with bromobenzene protected phenyl[D1]meth-
ylamines gave products of only 52–69% ee depending on the
solvent used. Tributyl(thio[D1]methyl)stannanes could not be
Stille-coupled with benzoyl chloride or with bromobenzene.
Similarly, dimethyl phenyl[D1]methylboronate underwent a
Suzuki–Miyaura coupling with bromobenzene to give phen-
yl[D1]methylsilane with 99% ee. All couplings followed a re-
tentive course and, except in one case, the intermediate
[XCHDPdLn] complexes were found to be microscopically
configurationally stable.
substituted methyllithium compounds[7] 1, and studied their
microscopic (on the time scale of a rearrangement) and
macroscopic (addition to benzaldehyde after aging) config-
urational stability (Figure 1). The substituent X comprised
oxygen-,[8] sulfur-,[9] and nitrogen-containing[10] moieties
and chloride[11] and bromide.[9] In summary, chiral meth-
yllithium compounds with oxygen as heteroatom were con-
figurationally stable at –78 °C or even higher temperatures,
whereas nitrogen-containing chiral methyllithium com-
pounds were only partly stable even at –95 °C. Chiral chlo-
ro- and bromo[D1]methyllithium are chemically very labile,
but configurationally stable.[11] This paper focuses on inter-
mediates of structural type 2 in palladium-catalyzed cross-
coupling reactions.
Introduction
Chiral, α-heteroatom-substituted organolithium com-
pounds that are configurationally stable (at low tempera-
tures) are valuable reagents for preparative, synthetic, ste-
reochemical, mechanistic, and theoretical reasons.[1] Still
and Sreekumar were the first to demonstrate that α-hetero-
atom-substituted alkyllithium compounds are configura-
tionally stable at low temperature. They found that α-alk-
oxyalkyllithium compounds can be generated easily from
the corresponding stannanes and that they react with elec-
trophiles.[2] This finding sparked a broad interest in α-het-
eroatom-substituted alkyllithium compounds. Just to name
three, the groups of Hoppe,[3] Beak,[4] and Hoffmann,[5] pi-
oneered this field and developed methods to prepare these
organolithium compounds enantioselectively and to deter-
mine their configurational stability. Although many theo-
retical calculations were performed on heteroatom-substi-
tuted methyllithium compounds as analogues for alkyllith-
ium compounds,[6] they were not evaluated experimentally,
because they were not accessible until recently. We concen-
trated on these most simple cases, the chiral α-heteroatom-
Figure 1. Chiral [D1]methyllithium compounds 1 and [D1]methyl-
palladium compounds 2.
[a] Institute of Organic Chemistry, University of Vienna,
Währingerstrasse 38, 1090 Vienna, Austria
E-mail: friedrich.hammerschmidt@univie.ac.at
Supporting information for this article is available on the
WWW under http://dx.doi.org/10.1002/ejoc.201300439.
© 2013 The Authors. Published by Wiley-VCH Verlag GmbH &
Co. KGaA.
Results and Discussion
This is an open access article under the terms of the Creative
Commons Attribution-NonCommercial License, which permits
use, distribution and reproduction in any medium, provided the
original work is properly cited and is not used for commercial
purposes.
To widen the scope for the preparation of compounds
containing an attached chiral XCHD substituent, we de-
cided to use the Stille cross-coupling[12] to transfer chiral
Eur. J. Org. Chem. 2013, 5143–5148
© 2013 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
5143

P. Malova Krizkova, F. Hammerschmidt
FULL PAPER
[D1]methyl groups. The required stannanes were either of [PhPdLn] and stannane to the reductive elimination of
known or could be obtained from (R)- and (S)-tributyl- phenylmethanol with regeneration of Pd0Ln.
stannyl[D1]methanol[8] in 99% ee. To use this transforma-
(Tributylstannyl)methyl benzoate (5) and both labeled
tion in more complex settings, the overall stereochemistry isotopomers and benzoyl chloride were coupled next
was first addressed with simple substrates. Because the Stille (Scheme 2).
coupling of (tributylstannyl)methanol and bromobenzene
with tetrakis(triphenylphosphane)palladium had previously
been studied[13] and the conditions had been optimized, we
repeated this experiment with the unlabeled and sub-
sequently with the labeled species (Scheme 1).
Scheme 1. Stille coupling of (tributylstannyl)methanols and PhBr
with Pd0Ln.
Scheme 2. Stille cross-coupling of (tributylstannyl)methyl benzo-
ates 5 with PhC(O)Cl.
As we were primarily interested in the stereochemical
outcome of the transfer of the chiral methyl group, the yield
of 38% for (R)-[D1]4 (57% for 4), although lower than the
Falck et al. found, that various acetates and benzoates of
yield previously[13] reported for 4 (83%), was not of major α-(tributylstannyl) alcohols can be cross-coupled with acyl
concern. When starting from stannylmethanol (S)-[D1]3, chlorides with retention of configuration, cocatalyzed by
the isolated deuterated benzyl alcohol and an authentic CuI salts.[17] However, Labadie and Stille reported that
sample of the (S) enantiomer[14] were converted into the phenyl-, alkyl-, and vinylstannanes could be coupled with
(R)-Mosher esters[15] using Mosher chloride [(S)-MTPACl]/ benzoyl chloride without using CuICN as cocatalyst.[18] The
1
pyridine. They were investigated by H NMR spectroscopy benzoates were easily accessible and were cross-coupled by
(400 MHz, CDCl3) to determine their de, which corre- the procedure reported in the literature.[17] To determine the
sponded to the ee of the underlying [D1]4, and the configu- configuration and ee at C-1 of esters 6 and (S)- and (R)-
1
ration of the alcohol obtained by coupling. The H NMR [D1]6, they were reduced with LiAlH4 to diol (Ϯ)-7 and
spectrum of the latter displayed a broadened singlet at δ = mixtures of diastereomeric diols (1RS,2R)- and (1RS,2S)-
5.33 ppm, whereas the 1H NMR spectrum of the (R)- [2-D1]7, respectively. The latter two mixtures were converted
Mosher ester of an authentic sample of (S)-phenyl[D1]- into mixtures of (R)-Mosher esters, having (S) and (R) con-
methanol displayed the signal for the CHD group at δ = figuration at C-2, respectively (C-2 of the diol corresponds
5.29 ppm (Figure 2). As we started from stannylmethanol to C-1 of the benzoylated hydroxy ketone [D1]6).[8a] For
(S)-[D1]3 and obtained deuterated phenylmethanol (R)- clarity, it is more convenient here and in similar cases to
[D1]4 with 99% ee, the Stille coupling clearly followed a net give the enantiomeric excess for each chiral center of diol
retentive course. On the basis of the accepted mecha- [2-D1]7 individually (“ee”). Because the reduction of [D1]6
nism,[16] the chiral complex [(HOCHD)PhPdLn] must there- is not enantioselective, the diol will be racemic at C-1 and
fore be configurationally stable at 80 °C from the formation therefore the “ee” at C-1 will be zero. The “ee” at C-2 of
1
Figure 2. H NMR signals of the CHD groups of the (R)-Mosher esters of (R)-phenyl[D1]methanol (left) and authentic (S)-phenyl[D1]-
methanol (right).
5144
www.eurjoc.org
© 2013 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Eur. J. Org. Chem. 2013, 5143–5148

Intermediates of Stille and Suzuki–Miyaura Cross-Coupling Reactions
both diols [D1]7 was higher than 99%, deduced from the amounts of alcohols 15 and (1RS,2S)-[2-D1]15 were ob-
1
“de” of more than 99% at C-2 as determined by H NMR tained for derivatization with (S)-Mosher chloride. The ee
spectroscopic analysis. Therefore, the Stille cross-coupling was found to be Ն 98% (1H NMR, 600 MHz, CDCl3). In
occurred with net retention of configuration, and the inter- analogy to the transfer of the chiral oxy[D1]methyl group
mediate chiral methylpalladium complex [{PhC(O)}Pd- by the Stille reaction, we assume net retention of configura-
{CHDOC(O)Ph}Ln] is microscopically configurationally tion also occurs for the aminomethyl group.
stable in toluene at 70 °C.
To see whether sulfur-substituted chiral methyl groups
can be transferred by the Stille reaction, the respective unla-
beled isomers of 10 and 11 were prepared and tested first
(Scheme 3). The sodium salt of benzylmercaptane (8) was
alkylated with mesylate[8b] 9 to yield sulfide 10.[9] The
thioacetate 11 was obtained in 84% yield by the Mitsunobu
reaction[19] of stannylmethanol 3 with thioacetic acid. We
attempted to cross-couple these two stannanes with either
benzoyl chloride or bromobenzene with 5 mol-% [(Ph3P)2-
PdCl2] either with or without CuCN (10 mol-%), [(Ph3P)4-
Pd] (5 mol-%), or [(tBu3P)2Pd] (3 mol-%)[20] in toluene at
temperatures up to 75 °C or dioxane up to 100 °C. No cou-
pling product could be detected, although 12a[21] and 12b[22]
Scheme 4. Stille reaction of N-[(tributylstannyl)methyl]phthal-
were prepared as reference samples for unequivocal detec-
imides 13 and (R)-[D1]13.
tion of the desired products by TLC and by 1H NMR spec-
troscopy. A part of the starting material could be recovered.
When the stannane was activated[20] with 2.2 equiv. of CsF
for transfer of the benzylthiomethyl group to PhBr, and
[(tBu3P)2Pd] was used as catalyst in dioxane as solvent, the
starting material was consumed after 25 h at 90 °C. How-
ever, the desired product could not be detected in the crude
material. On the other hand, a compound derived from the
stannane by loss of two butyl groups, reminiscent of find-
ings by Stille[18] and Falk,[17] was found.
Finally, benzoyl chloride was replaced by bromobenzene
in the Stille coupling (Scheme 5). Despite optimization of
the reaction conditions in the unlabeled series by using vari-
ous combinations of a Pd catalyst either alone or with
CuCN as cocatalyst and toluene or dioxane as solvent, the
yield was 37% at best (Table 1). Rather high quantities of
Pd catalyst (8 mol-%) and CuCN (16 mol-%) were required,
and the solvent did not seem to influence the yield (En-
tries 3 and 4). The use of [{(tBu)3P}2Pd] as catalyst either
alone or in combination with CsF did not give any coupling
product. The chiral stannanes (R)- and (S)-[D1]13 were cou-
pled under identical conditions, except that dioxane and tol-
uene were used, respectively (Entries 5 and 6). Hydrazino-
lysis of phthalimides 16 gave benzylamines 17, which were
Scheme 3. Preparation of starting materials 10 and 11 and at-
tempted Stille coupling.
Finally, we studied the transfer of the N-protected
aminomethyl and chiral amino[D1]methyl groups from
known stannanes[10] 13 and (R)-[D1]13 with benzoyl chlor-
ide or bromobenzene as our standard organic halides. The
cross-coupling in toluene with [(Ph3P)4Pd] and benzoyl
chloride was a smooth reaction, giving N-protected amino
ketones 14 and an impurity, which could be removed by
flash chromatography, assuming (preferential) transfer of
the aminomethyl group with retention of configuration
(Scheme 4). To evaluate the ee at the stereogenic center, the
sluggish catalytic reduction of a reference sample of 14 with
a large amount of catalyst was first performed a few times.
Scheme 5. Stille reaction of N-[(tributylstannyl)methyl]phthal-
Although the reproducibility of the yield was low, sufficient imides 13 and bromobenzene.
Eur. J. Org. Chem. 2013, 5143–5148
© 2013 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
5145

P. Malova Krizkova, F. Hammerschmidt
FULL PAPER
Figure 3. Signals of the CHD group in the 1H NMR spectra (400 MHz) of (R)-Mosher amides derived from (S)-[D1]16 (left, 69% ee)
and authentic (R)-[D1]16 (right, 99% ee).
derivatized with (S)-MTPACl to furnish amides that were terated and deuterated form from boronates 18 and (S)-[D1]-
1
suitable for the determination of the ee by H NMR spec- 18, respectively. The silanes would be converted into phenyl-
troscopy. An authentic sample of (R)-phenyl[D1]methyl- methanols 4 by the Tamao–Kumada–Fleming oxidation.[26]
amine [(R)-[D1]16] was prepared from (S)-phenyl[D1]meth- Surprisingly, the coupling of boronate 18 with excess bro-
anol and converted into the (R)-Mosher amide. The 1H mobenzene (3 equiv.) using [(Ph3P)4Pd] (5 mol-%) as cata-
NMR spectra (400 MHz) show that stannanes (R)- and (S)- lyst was a slow transformation. The reaction temperature
[D1]13 gave labeled N-benzylphthalimides of the same con- had to be maintained at 90 °C and the reaction time at 18 h
figuration, implying a net retentive course for the coupling. to obtain a yield of 59% of silane 19. Biphenyl was formed
However, the enantiomeric excesses were 52% (dioxane as as an unexpected side product in 15% yield by transferring
solvent) and 69% (toluene as solvent), respectively (Fig- the phenyl group from the silicon atom.[27] The best way to
ure 3). Suginome et al. performed Suzuki–Miyaura cou- convert coupling product 19 into phenylmethanol (4), was
plings of enantioenriched [α-(acylamino)benzyl]boronic es- first treatment with HBF4·Et2O to rapidly generate silyl
ters (acyl = acetyl, propionyl, benzoyl, pivaloyl) with aryl fluoride 20 in high yield,[28] then oxidation[29] of the crude
chlorides and bromides.[23] However, they found that the product to 4 in 67% yield.
formation of the C–C bond was highly stereospecific and
followed an invertive course. This was attributed to a transi-
tion state for transmetalation with a strong intramolecular
coordination of the carbonyl group to the boron atom,
which is not possible in stannanes 13.
Table 1. Stille reaction of (aminomethyl)stannanes 13 with bromo-
benzene.
Entry Stannane
Catalyst (mol-%) Solvent
Cocatalyst (mol-%)
T
[°C]
t
[h]
Yield
[%]
1
13
[(Ph3P)2PdCl2] (4) toluene
CuCN (8)
80
20
13
2
3
13
13
[(Ph3P)4Pd] (5)
[(Ph3P)2PdCl2] (8) toluene 110
CuCN (16)
[(Ph3P)2PdCl2] (8) dioxane 100
CuCN (16)
dioxane
80
20
6
14
37
Scheme 6. Suzuki–Miyaura reaction of boronates 18 and (S)-[D1]
18.
4
5
6
13
6
3
3
37
29
53
Similarly, boronate (S)-[D1]18 furnished [D1]4 in 99% ee
with (S) configuration, as determined by 1H NMR spectro-
scopic analysis of its (R)-Mosher ester. This result implies
that the chiral [(dimethylphenyl)silyl]methyl group was
transferred with net retention of configuration and that the
(R)-[D1]13 [(Ph3P)2PdCl2] (8) dioxane
CuCN (16)
(S)-[D1]13 [(Ph3P)2PdCl2] (8) toluene
CuCN (16)
90
90
An alternative to (tributylstannyl)[D1]methanol as a syn- intermediate palladium complex [{(PhMe2Si)CHD}-
thetic equivalent of chiral CHDOH is boronate (S)-[D1]- PdPhLn] was configurationally stable during its (suppos-
18,[24] which is more easily accessible than the former com- edly) short life-time. These results are in line with studies
pound (Scheme 6). To study the feasibility of the given se- published by Crudden et al.,[30] who demonstrated that Pd-
quence, we tested the Suzuki–Miyaura reaction[25] for trans- catalyzed cross coupling of chiral secondary benzylboronic
ferring the [(dimethylphenyl)silyl]methyl group in non-deu- esters followed a retentive course.
5146
www.eurjoc.org
© 2013 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Eur. J. Org. Chem. 2013, 5143–5148

Intermediates of Stille and Suzuki–Miyaura Cross-Coupling Reactions
The first step in the Stille and the Miyaura–Suzuki reac-
tion is the oxidative addition of PdLn to PhBr or PhC(O)-
Cl, followed by transmetalation with either a stannane or
boronate to give intermediates [(XCHD)PdYLn] [X = OH,
PhCO2, PhthN and Y = Ph or PhC(O) or X = PhMe2Si, Y
= Ph]. As we find net retention of configuration for the
coupling, transmetalation must occur via a cyclic closed
transition state with retention of configuration, because re-
ductive elimination follows a retentive course. In the case of
transmetalation of [PhC(O)PdLn] with N-[(tributylstannyl)-
methyl]phthalimides 13, either an open transition state in-
terferes with the closed transition state, or the closed transi-
Acknowledgments
The research was funded by the Austrian Science Fund (FWF)
through Grant No. P19869-N19. We thank A. Wieczorek for the
preparation of stannane 10, boronate (S)-[D1]18, and for the refer-
ence spectrum of the Mosher ester (S)-[D1]4. We thank S. Felsinger
for recording NMR spectra and J. Theiner for performing combus-
tion analyses.
[1] a) J. Clayden, Tetrahedron Org. Chem. Ser. 2002, 23; b) D. M.
Hodgson, Top. Organomet. Chem. 2003, 5; c) R. E. Gawley,
Top. Stereochem. 2010, 26; d) V. Capriati, S. Florio, Chem. Eur.
J. 2010, 16, 4152–4162.
tion state is not microscopically configurationally stable, [2] W. C. Still, C. Sreekumar, J. Am. Chem. Soc. 1980, 102, 1201–
which is more pronounced in dioxane than in toluene. Ac-
cordingly, the ee is lowered from the usual 99% to 52 and
69%, respectively.
1202.
[3] T. Hemery, R. Huenerbein, R. Froehlich, S. Grimme, D.
Hoppe, J. Org. Chem. 2010, 75, 5716–5720.
[4] W. K. Lee, Y. S. Park, P. Beak, Acc. Chem. Res. 2009, 42, 224–
234.
[5] R. W. Hoffmann, Top. Stereochem. 2010, 26, 165–188.
[6] G. Boche, J. C. W. Lohrenz, Chem. Rev. 2001, 101, 697–756.
Conclusions
[7] a) A reviewer pointed out that the designation of a methyl
group as “chiral” or “asymmetric” has been exclusively restric-
We have used the Stille and, in one case, also the Suzuki–
Miyaura cross-coupling to transfer chiral heteroatom-sub-
stituted [D1]methyl groups to bromobenzene and benzoyl
chloride. [(Ph3P)4Pd] or [(Ph3P)2PdCl2], either alone or in
combination with CuICN as cocatalyst were used as cata-
lysts. These reactions follow a net retentive course, yielding
products with 99% ee; only the coupling of N-[(tributyl-
stannyl)[D1]methyl]phthalimide with bromobenzene gave
products with 52–69% ee, depending on the solvent used.
Therefore, except for the latter case, the intermediate chiral
[XCHDPdLn] complexes must be microscopically configu-
rationally stable (relative to reductive elimination). The re-
sults presented here, in combination with the previous stud-
ies with lithium, show nicely that the configurational sta-
bility of XCHD–metal compounds is very much dependent
on the metal used.
ted to CHDT as has been stated by K. Mislow. We think that
chiral methyllithium compounds, chiral [D1]methyllithium
compounds, chiral heteroatom-substituted methyllithium com-
pounds, etc. are generic names that do not imply stereochemi-
cal aspects, which should be allowed. Furthermore, is that re-
striction of chiral methyl group to CHDT really any longer
useful and justified? b) K. Mislow, J. Siegel, J. Am. Chem. Soc.
1984, 106, 3319–3328.
[8] a) D. C. Kapeller, R. Barth, K. Mereiter, F. Hammerschmidt,
J. Am. Chem. Soc. 2007, 129, 914–923; b) D. C. Kapeller, L.
Brecker, F. Hammerschmidt, Chem. Eur. J. 2007, 13, 9582–
9588; c) D. C. Kapeller, F. Hammerschmidt, J. Org. Chem.
2009, 74, 2380–2388; d) D. C. Kapeller, F. Hammerschmidt,
Tetrahedron 2010, 66, 591–598.
[9] A. Wieczorek, F. Hammerschmidt, J. Org. Chem. 2012, 77,
10021–10034.
[10] D. C. Kapeller, F. Hammerschmidt, Chem. Eur. J. 2009, 15,
5729–5739.
[11] D. C. Kapeller, F. Hammerschmidt, J. Am. Chem. Soc. 2008,
130, 2329–2335.
[12] a) J. K. Stille, Angew. Chem. 1986, 98, 504–519; Angew. Chem.
Int. Ed. Engl. 1986, 25, 508–524; b) T. N. Mitchell, Synthesis
1992, 803–815.
[13] M. Kosugi, T. Sumiya, K. Ohhashi, H. Sano, T. Migita, Chem.
Lett. 1985, 14, 997–998.
Experimental Section
Stille Coupling of Bromobenzene with (Tributylstannyl)methanol (3)
and (S)-(Tributylstannyl)[D1]methanol [(S)-[D1]3]: Anhydrous 1,4-
dioxane (4 mL) and bromobenzene (0.141 g, 0.9 mmol, 0.094 mL)
were added to (tributylstannyl)methanol (3; 0.435 g, 1.35 mmol)
and [Pd(PPh3)4] (0.052 g, 0.045 mmol) under argon at room tem-
perature.[8] The mixture was stirred at 80 °C for 18 h. After cooling
to room temperature, the mixture was concentrated under reduced
pressure and purified by flash chromatography (hexane/EtOAc, 5:1;
Rf = 0.32) to give phenylmethanol (4; 0.055 g, 57%) as a colorless
liquid. 1H NMR (400.13 MHz, CDCl3): δ = 7.36–7.32 (m, 4 H),
7.30–7.25 (m, 1 H), 4.67 (s, 2 H) ppm. 13C NMR (100.61 MHz,
CDCl3): δ = 140.9, 128.6 (2 C), 127.7, 127.0 (2 C), 65.4 ppm. Simi-
larly, (S)-(tributylstannyl)[D1]methanol {(S)-[D1]3; 0.312 g,
0.97 mmol} was converted into (R)-phenyl[D1]methanol {(R)-[D1]-
4; 0.040 g, 38%}. 1H NMR (400.27 MHz, CDCl3): δ = 7.38–7.33
(m, 4 H), 7.32–7.25 (m, 1 H), 4.66 (t, J = 1.8 Hz, 1 H, CHD) ppm.
[14] R. H. Wightman, J. Staunton, A. R. Battersby, K. R. Hanson,
J. Chem. Soc. Perkin Trans. 1 1972, 2355–2364.
[15] J. M. Seco, K. Quiñoá, R. Riguera, Chem. Rev. 2004, 104, 17–
118.
[16] P. Espinet, A. M. Echavarren, Angew. Chem. 2004, 116, 4808–
4839; Angew. Chem. Int. Ed. 2004, 43, 4704–4734.
[17] J. Ye, R. K. Bhatt, J. R. Falk, J. Am. Chem. Soc. 1994, 116, 1–
5.
[18] J. W. Labadie, J. K. Stille, J. Am. Chem. Soc. 1983, 105, 6129–
6137.
[19] K. C. Kumara Swamy, N. N. Bhuvan Kumar, E. Balaraman,
K. V. P. Pavan Kumar, Chem. Rev. 2009, 109, 2551–2651.
[20] A. F. Littke, L. Schwarz, G. C. Fu, J. Am. Chem. Soc. 2002,
124, 6343–6348.
[21] H. Loghmani-Khouzani, M. R. Poorheravi, M. M. M. Sad-
eghi, L. Caggiano, R. F. W. Jackson, Tetrahedron 2008, 64,
7419–7425.
[22] R. S. Givens, B. Hrinczenko, J. H. S. Liu, B. Matuszewski, J.
Tholen-Collison, J. Am. Chem. Soc. 1984, 106, 1779–1789.
[23] T. Ohmura, T. Awano, M. Suginome, J. Am. Chem. Soc. 2010,
132, 13191–13193.
Supporting Information (see footnote on the first page of this arti-
cle): General information, detailed experimental procedures and
1
copies of the H and 13C NMR spectra of products.
Eur. J. Org. Chem. 2013, 5143–5148
© 2013 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjoc.org
5147

P. Malova Krizkova, F. Hammerschmidt
FULL PAPER
[24] B. P. Simov, F. Wuggenig, K. Mereiter, H. Andres, J. France, P.
Schnelli, F. Hammerschmidt, J. Am. Chem. Soc. 2005, 127,
13934–13940.
[27] S. E. Denmark, M. H. Ober, Aldrichim. Acta 2003, 36, 75–85.
[28] I. Fleming, R. Henning, D. C. Parker, H. E. Plaut, P. E. J. San-
derson, J. Chem. Soc. Perkin Trans. 1 1995, 317–337.
[29] H.-J. Knölker, G. Wanzl, Synlett 1995, 378–382.
[30] D. Imao, B. W. Glasspoole, V. S. Laberge, C. M. Crudden, J.
Am. Chem. Soc. 2009, 131, 5024–5025.
[25] a) N. Miyaura, A. Suzuki, Chem. Rev. 1995, 95, 2457–2483; b)
F.-X. Felpin, T. Ayad, S. Mitra, Eur. J. Org. Chem. 2006, 2679–
2690; c) M. Tobisu, N. Chatani, Angew. Chem. 2009, 121, 3617;
Angew. Chem. Int. Ed. 2009, 48, 3565–3568.
Received: March 25, 2013
[26] G. R. Jones, Y. Landais, Tetrahedron 1996, 52, 7599–7662.
Published Online: June 27, 2013
5148
www.eurjoc.org
© 2013 The Authors. Published by Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Eur. J. Org. Chem. 2013, 5143–5148