Manganese-Catalyzed Direct Olefination of Methyl-Substituted Heteroarenes with Primary Alcohols

Article abstract of DOI:10.1002/anie.201804729

Herein, we present the first catalytic direct olefination of methyl-substituted heteroarenes with primary alcohols through an acceptorless dehydrogenative coupling. The reaction is catalyzed by a complex of the earth-abundant transition metal manganese that is stabilized by a bench-stable NNN pincer ligand derived from 2-hydrazinylpyridine. The reaction is environmentally benign, producing only hydrogen and water as byproducts. A large number of E-disubstituted olefins were selectively obtained with high efficiency.

Full text of DOI:10.1002/anie.201804729

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Accepted Article
Title: Manganese Catalyzed Direct Olefination of Methylheteroarenes
with Primary Alcohols
Authors: Milan K. Barman, Satyadeep Waiba, and Biplab Maji
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To be cited as: Angew. Chem. Int. Ed. 10.1002/anie.201804729
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Angewandte Chemie International Edition
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COMMUNICATION
Manganese Catalyzed Direct Olefination of Methylheteroarenes
with Primary Alcohols
Milan K. Barman, Satyadeep Waiba, and Biplab Maji*
Dedicated to Professor David Milstein on the occasion of his 70th birthday
Abstract: Herein, we present the first example of catalytic direct
olefination of methylheteroarenes using primary alcohols via
methanol to CO
2
and H
2
,[18] dehydrogenative N-formylations of
amines,[19] coupling of alcohols to esters, synthesis of imines,[21]
[20]
quinolines,[22] pyrimidines,[22-23] pyrroles,
[24]
cyclic imides,[25]
acceptorless
dehydrogenative
coupling
of
alcohols
and
amides,[26] and, α,β-unsaturated nitriles and hydrogenations of
[27]
methylheteroarenes. The reaction is catalyzed by an Earth’s abundant
transition metal (manganese) stabilized by a bench stable NNN-pincer
ligand derived from 2-hydrazinylpyridine. The reaction is highly
environmentally benign producing only hydrogen and water as
polar double bonds.[
28]
Employing ‘borrowing hydrogenations’
methodology C-alkylation of ketones[29] and N-alkylation of
amines[30] have also been reported.
byproducts.
A
large number of (E)-disubstituted olefins were
With these recent advancements, we have recently considered
selectively obtained in high efficiency.
whether
the
Mn-catalyzed
ADC
of
alcohols
with
methylheteroarenes can present an alternative direct route for the
synthesis of stilbenoids (Scheme 1). This method will be highly
sustainable and advantageous because; (1) The alcohols are
readily available from several industrial processes or can be
obtained from renewable resources via fermentation or catalytic
conversion of lignocellulosic biomass.[31] (2) Only hydrogen and
water will be produced as byproducts. (3) Functional group
manipulations can be avoided. However, the challenge
associated with the activation of weakly acidic C–H bond[32] in
conjugation with the Mn-catalyzed dehydrogenation process has
Olefins, in particular conjugated (E)-disubstituted alkenes are
valuable building blocks.[1] Many styryl derivatives display a wide
range of biological activities including prevention of cancer and
cardiovascular diseases[2] and are also act as in vivo imaging
agents and sensors.[3] They are also among the most used class
of materials in organic functional dyes applied as sensitizer,
electroluminescence, and photochromism.[4]
The carbonyl olefinations using carbanions decorated with a
leaving group have traditionally been utilized for the syntheses of
styryl derivatives.[5] Depending upon the leaving group, for
to be kept in considerations.
In fact, previously reported Ir-,
[33]
and Ru-,[34] and Pt-catalyzed[35]
[6]
example PR
Emmons reaction),[7] SiR
(Peterson olefination), SO R (Julia
3 2
3
(Witting reaction), P(O)(OR)
2
(Horner-Wadsworth-
reactions of methylheteroarenes with primary alcohols yields
alkylations products (Scheme 1). However, to our knowledge,
[8]
olefination)[9] etc., these reactions comprise very powerful
synthetic tools. Catalytic Heck, Suzuki coupling[10] or more
recently olefin metathesis[11] constitute more efficient strategy for
the synthesis of stilbenoids. However, multi-step functional group
manipulations and unavoidable productions of stoichiometric
amount of waste are few limitations in all such reactions.
transition
metal
catalyzed
ADC
of
alcohols
and
methylheteroarenes to form (E)-disubstituted alkenes with the
liberation of hydrogen and water have not been reported so far.
Acceptorless dehydrogenative coupling (ADC) of alcohols have
become a powerful technique for the synthesis of unsaturated
compounds.[12] Over the last few decades, the advancement of
such reactions have been made with precious and toxic noble
metal based catalysts.[13] However, their replacement with Earth’s
abundant metals (Mn, Fe, Co, Ni) is desirable not only in terms of
economic constrains and sustainability but also for the exploration
of new reactivities[14] and significant advancement has been made
Scheme 1. Transition metal catalyzed dehydrogenative coupling of alcohols
with methylheteroarenes.
for the ADC reactions.[15] In this regard, manganese being third
most abundant transition metal has appeared as an attractive
alternative.[16] In 2016, Milstein et al. have reported first example
of Mn-catalyzed ADC of alcohols with amines.[17] Subsequently,
Mn-complexes have utilized for catalytic dehydrogenations of
Table1 illustrates an abbreviated optimization table for the Mn-
catalyzed direct dehydrogenative olefination reaction using 2-
methylpyrazine 1a with benzyl alcohol 2a (see the SI for details).
Inspired by the recent studies, we have realized that in situ
catalyst formation with cheap, readily available and bench stable
nitrogen donner ligands would enable more rapid
optimization.[28j,f,m,36-37] As with those findings, the hydrazone
based pincer ligand L6[40] was found to be ideal delivering the
product (E)-2-styrylpyrazine 3aa in 96% yield (Table 1, entry 6).
The reaction was also found to be very selective; the undesired
[*]
Dr. M. K. Barman, M.Sc. S. Waiba, Prof. Dr. B. Maji
Department of Chemical Sciences
Indian Institute of Science Education and Research Kolkata
Mohanpur 741246, India
E-mail: bm@iiserkol.ac.in
Web: http://biplabmaji.wixsite.com/iiserkol
Supporting information for this article is given via a link at the end of
the document.
(
Z)-3aa and the reduced product 2-phenethylpyrazine 3aa’ could
not be detected by GC-MS analysis. To note, the ligands L1 and
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COMMUNICATION
L2 have previously been shown to be highly efficient for the
transfer hydrogenation of carbonyls by Sortais[28i,m] and Beller.[28j]
Control experiments demonstrated the necessity of Mn(I)-salt, L6,
and t-BuOK as only traces of the products were formed in their
absence (entry 7). The catalyst loading to 2.5 mol% and the
amount of 2a could be lowered to 1.2 equivalent without any
change in yield (entry 8).
the reducible halogen functional group is retained in the products.
Alcohols containing hetero aromatic groups such as 3-pyridyl
(2m), 2-pyridyl (2n), 2-thiophenyl (2o), and 2-furyl (2p) were also
found to be viable coupling partner. Same result was obtained for
strained cyclopropylmethanol (2q). The reaction of 2r went
sluggishly and 39% of the desired product was obtained after 24h.
Likewise reactivity was also observed for the linear alcohols such
as n-butanol 2s and n-hexanol 2t. However, the 4-substituted
benzyl alcohols containig cyano, carboxyethyl, and nitro groups
were currently found to be unsuitable coupling partners.
Table 1. Optimization: Mn-catalyzed olefination of 2-methylpyrazine 1a with
[
a]
benzyl alcohol 2a.
The synthetic utility of this ADC reaction was showcased by
applying it for the synthesis of STB-8, a specific in vivo imaging
agent for Alzheimer’s disease β-amyloid plaques (Table 2).[
STB-8 is also the core structure of 2E10, a green imaging agent
of amyloid deposits.[3a,c] The ADC reaction was also applied for
the synthesis of the core structures of Heparin-blue which is used
as chemical sensor for heparin[3a,d] and the drug Montelukast
which is used for the treatment of asthma and to relieve
symptoms of seasonal allergies.[39]
3a,b]
Following the evaluation of the scope, we turn our attention to
prepare the manganese precatalyst. The treatment of Mn(CO)
with L6 (1 equiv.) in toluene at 80 C resulted in the formation of
5
Br
o
a mixture of cationic and neutal complex in approximately equal
ratio (see the SI for details).[
30d]
To test the nature of the active
Br/L6 complex
manganese catalyst, the in situ generated Mn(CO)
5
was reacted with an excess amount of t-BuOK. The produced
orange solution was characterized by IR and NMR.[
Importantly, the solution was found to catalyze the ADC reaction
with equal efficiency.
28a,g,i,j]
[
[
a]
c]
.1 mmol. [b]Determined by GC-MS analysis of the crude mixture.
Selectivity = Ratio of 3aa/[(Z)-3aa+3aa’]. Isolated yield.
0
[d]
Then, to probe the hydrogen gas evolution, hydrogenation of
styrene was carried out using Pd/C catalyst using the liberated H
during Mn-catalyzed ADC reaction in an H-shaped bridged tube
see the SI for details). In a typical experiment, the olefination
reaction was carried out in one vial and the other chamber
contains styrene and Pd/C. The H liberated in the first flask
2
With these optimized conditions in hand, we explored the scope
of this olefination reaction (Table 2). We are delighted to find that
the high efficiency shown by the Mn(CO) Br/L6 catalyst system in
5
the model reaction can also be applied to a larger number of
methylheteroarenes 1a-n using 2a as coupling partner. In all
cases, complete complementary selectivity for the olefination
reaction was observed.[33-35] (E)-4-styrylpyrimidine derivatives
(
2
during the ADC of 2y was found to reduce styrene present in the
second flask.
Next, the key condensation reaction between 1a with
benzaldehyde was carried out in absence and presence of
Mn(I)/L6 to probe its high catalytic activity (Table 3). The catalyst-
free reaction shows a ratio of 1:0.82 between 1a and 3aa after 3h.
In comparison, the Mn(I)/L6 catalyst system displays a 7-fold
increase in reactivity (1a/3aa = 1:5.7) under the same condition.
3ba and 3ca were obtained in 86% and 95% yields, respectively
when 4-methyl pyrimidine derivatives 1b,c were subjected to this
ADC reaction. The reaction of 2-picoline derivatives 1d,e with
benzyl alcohol was sluggish and the products were obtained in
3
6% and 34% yields, respectively after 36 h. However, only traces
of product was observed for 1f. Pleasingly, 1g and its derivatives
h,1 were olefinated in high yields. The reaction could also be
1
performed in gram scale (1.27g, 79% yield) highlighting the
synthetic utility and practicality. The reactions of 1j and 1k were
also proceeded smoothly delivering the corresponding olefins in
Table 3. Control experiments.
76% and 91% yield, respectively. When 1l was used as substrate
mixed alkylation-olefination took place and the product 3la was
isolated in moderate yield. The reactions of 1m and its derivative
1n were completed in 14 h and the products 3ma and 3na were
isolated in 89% and 71% yields, respectively.
Next, the scope of the primary alcohols was evaluated. As shown
in Table 3, a large number of primary alcohols 2b-z with different
steric and electronic properties were tolerated. Strikingly, the
reaction is tolerant to fluoro-, chloro-, bromo-, iodo-, and
trifluoromethyl substituents on benzyl alcohols (2g-l). Except, for
[a]Determined by GCMS analysis.
Even a 2-fold increased reactivity was observed under the
Mn(I)/L6 catalyzed ADC condition using 2a. This result indicates
that the Mn-catalyst in addition to the catalytic dehydrogenation
2i where partial dehalogenation was observed, in all these cases,
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Table 2. Scope of Mn-catalyzed olefination reactions.[a]
[
a]Reaction conditions: See Table 1, Entry 8. [b]0.40 mmol of 2a was used. [c]GC yield. [d]0.48 mmol of 2a was used. [e] 7.50 mmol scale. [f]32% dehalogenated
product was observed. [g]t-BuOK 0.60 mmol was used.
step is also involve in the key C–C bond forming condensation
step. Similar, Mn-catalyzed substrate activation was previously
been observed for the reactions of benzyl cyanide with Michael
acceptors.[40]
In summary, we have developed an unprecedented transition
metal catalyzed dehydrogenative coupling of alcohol and
methylherehoarenes to form (E)-disubstituted alkenes. The
reaction proceed under environmentally friendly manner
producing water and hydrogen as byproducts. Moreover, a
complex of an earth’s abundant metal (Mn) and a readily available
(PDF/2016/001952) for an NPDF fellowship. S.W. thanks CSIR
for PhD fellowship.
Keywords: manganese • acceptorless-dehydrogenative-
coupling • pincer ligand • olefination • heteroarenes
[
1]
S. Matar, L. F. Hatch, Chemistry of Petrochemical Processes, Gulf
Professional Publishing, Houston, Texas, 2001.
[2]
(a) D. Simoni, M. Roberti, F. P. Invidiata, E. Aiello, S. Aiello, P. Marchetti,
R. Baruchello, M. Eleopra, A. Di Cristina, S. Grimaudo, N. Gebbia, L.
Crosta, F. Dieli, M. Tolomeo, Bioorg. Med. Chem. Lett. 2006, 16, 3245;
NNN-pincer ligand was utilized as catalyst.
A variety of
(b) K. Hagiwara, N. Kosaka, Y. Yoshioka, R.-u. Takahashi, F. Takeshita,
methylheteroarens and alcohols were employed to yield olefins in
moderate to high yields. The developed protocol significantly
broadens the scope of manganese catalyzed dehydrogenative
coupling reaction for the syntheses of unsaturated compounds.
T. Ochiya, Scientific Reports 2012, 2, 314; (c) J.-C. Jung, E. Lim, Y. Lee,
J.-M. Kang, H. Kim, S. Jang, S. Oh, M. Jung, Eur. J. Med. Chem. 2009,
4
4, 3166; (d) J. Dai, Z.-Q. Liu, X.-Q. Wang, J. Lin, P.-F. Yao, S.-L. Huang,
T.-M. Ou, J.-H. Tan, D. Li, L.-Q. Gu, Z.-S. Huang, J. Med. Chem. 2015,
8, 3875.
5
[
3]
(a) N.-Y. Kang, H.-H. Ha, S.-W. Yun, Y. H. Yu, Y.-T. Chang, Chem. Soc.
Rev. 2011, 40, 3613; (b) Q. Li, J. Min, Y.-H. Ahn, J. Namm, E. M. Kim, R.
Lui, H. Y. Kim, Y. Ji, H. Wu, T. Wisniewski, Y.-T. Chang, ChemBioChem
Acknowledgements
2
007, 8, 1679; (c) Q. Li, J. S. Lee, C. Ha, C. B. Park, G. Yang, W. B. Gan,
The author thanks IISER Kolkata (Start-up grant) and SERB
Y. T. Chang, Angew. Chem. Int. Ed. 2004, 43, 6331; (d) S. Wang, Y.-T.
Chang, Chem. Commun. 2008, 1173.
(
ECR/2016/001654) for financial support. M.K.B. thanks SERB
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[
4]
(a) A. Kraft, A. C. Grimsdale, A. B. Holmes, Angew. Chem. Int. Ed. 1998,
[25] N. A. Espinosa-Jalapa, A. Kumar, G. Leitus, Y. Diskin-Posner, D. Milstein,
J. Am. Chem. Soc. 2017, 139, 11722.
37, 402; (b) B. Nohra, S. Graule, C. Lescop, R. Réau, J. Am. Chem. Soc.
2
006, 128, 3520; (c) L.-Y. Wang, Q.-W. Chen, G.-H. Zhai, Z.-Y. Wen, Z.-
[26] A. Kumar, N. A. Espinosa-Jalapa, G. Leitus, Y. Diskin-Posner, L. Avram,
D. Milstein, Angew. Chem. Int. Ed. 2017, 56, 14992.
X. Zhang, Dyes and Pigments 2007, 72, 357.
[
[
[
5]
6]
7]
R. Dumeunier, I. E. Markó, in Modern Carbonyl Olefination: Methods and
Applications (Ed.: T. Takeda), Wiley-VCH, Weinheim, 2004.
(a) G. Wittig, G. Geissler, Justus Liebigs Ann. Chem. 1953, 580, 44; (b)
B. E. Maryanoff, A. B. Reitz, Chem. Rev. 1989, 89, 863.
[27] S. Chakraborty, U. K. Das, Y. Ben-David, D. Milstein, J. Am. Chem. Soc.
2017, 139, 11710.
[28] (a) S. Elangovan, C. Topf, S. Fischer, H. Jiao, A. Spannenberg, W.
Baumann, R. Ludwig, K. Junge, M. Beller, J. Am. Chem. Soc. 2016, 138,
8809; (b) V. Papa, J. R. Cabrero-Antonino, E. Alberico, A. Spanneberg,
K. Junge, H. Junge, M. Beller, Chem. Sci. 2017; (c) F. Kallmeier, T.
Irrgang, T. Dietel, R. Kempe, Angew. Chem. Int. Ed. 2016, 55, 11806; (d)
M. B. Widegren, G. J. Harkness, A. M. Z. Slawin, D. B. Cordes, M. L.
Clarke, Angew. Chem. Int. Ed. 2017, n/a; (e) N. A. Espinosa-Jalapa, A.
Nerush, L. J. Shimon, G. Leitus, L. Avram, Y. Ben-David, D. Milstein,
Chemistry 2016, n/a; (f) R. van Putten, E. A. Uslamin, M. Garbe, C. Liu,
A. Gonzalez-de-Castro, M. Lutz, K. Junge, E. J. M. Hensen, M. Beller, L.
Lefort, E. A. Pidko, Angew. Chem. Int. Ed. 2017, 56, 7531; (g) A. Dubey,
L. Nencini, R. R. Fayzullin, C. Nervi, J. R. Khusnutdinova, ACS Catal.
2017, 7, 3864; (h) S. Kar, A. Goeppert, J. Kothandaraman, G. K. S.
Prakash, ACS Catal. 2017, 7, 6347; (i) A. Bruneau-Voisine, D. Wang, V.
Dorcet, T. Roisnel, C. Darcel, J.-B. Sortais, Org. Lett. 2017, 19, 3656; (j)
M. Perez, S. Elangovan, A. Spannenberg, K. Junge, M. Beller,
ChemSusChem 2017, 10, 83; (k) A. M. Tondreau, J. M. Boncella,
Organometallics 2016, 35, 2049; (l) A. Bruneau-Voisine, D. Wang, T.
Roisnel, C. Darcel, J.-B. Sortais, Catal. Commun. 2017, 92, 1; (m) D.
Wang, A. Bruneau-Voisine, J.-B. Sortais, Catal. Commun. 2018, 105, 31.
[29] M. Pena-Lopez, P. Piehl, S. Elangovan, H. Neumann, M. Beller, Angew.
Chem. Int. Ed. 2016, 55, 14967.
(a) L. Horner, H. Hoffmann, H. G. Wippel, G. Klahre, Chem. Ber. 1959,
92, 2499; (b) J. Clayden, S. Warren, Angew. Chem. Int. Ed. 1996, 35,
241.
[
8]
9]
(a) D. J. Peterson, J. Org. Chem. 1968, 33, 780; (b) L. F. v. Staden, D.
Gravestock, D. J. Ager, Chem. Soc. Rev. 2002, 31, 195.
[
[
(a) M. Julia, J.-M. Paris, Tetrahedron Lett. 1973, 14, 4833
10] (a) R. F. Heck, J. P. Nolley, J. Org. Chem. 1972, 37, 2320; (b) K. Ferré-
Filmon, L. Delaude, A. Demonceau, A. F. Noels, Coord. Chem. Rev.
2004, 248, 2323.
[
[
[
11] (a) in Handbook of Metathesis, Vol. 1, 2, 3 (Ed.: R. H. Grubbs), Wiley-
VCH, Weinheim, 2003.
12] (a) C. Gunanathan, D. Milstein, Science 2013, 341; (b) R. H. Crabtree,
Chem. Rev. 2017, 117, 9228.
13] (a) D. Benito-Garagorri, K. Kirchner, Acc. Chem. Res. 2008, 41, 201; (b)
J. Choi, A. H. R. MacArthur, M. Brookhart, A. S. Goldman, Chem. Rev.
2011, 111, 1761; (c) N. Selander, K. J. Szabo, Chem. Rev. 2011, 111,
2048; (d) C. Gunanathan, D. Milstein, Chem. Rev. 2014, 114, 12024.
[
[
14] R. M. Bullock, Catalysis without Precious Metals, Wiley-VCH, Weinheim,
010.
2
15] (a) T. Zell, D. Milstein, Acc. Chem. Res. 2015, 48, 1979; (b) P. J. Chirik,
Acc. Chem. Res. 2015, 48, 1687; (c) R. M. Bullock, Science 2013, 342,
[30] (a) S. Elangovan, J. Neumann, J.-B. Sortais, K. Junge, C. Darcel, M.
Beller, Nat. Commun. 2016, 7, 12641; (b) J. Neumann, S. Elangovan, A.
Spannenberg, K. Junge, M. Beller, Chem. Eur. J. 2017, 23, 5401; (c) A.
Bruneau-Voisine, D. Wang, V. Dorcet, T. Roisnel, C. Darcel, J.-B. Sortais,
J. Catal. 2017, 347, 57. (d) A. M. Tondreau, J. M. Boncella, Polyhedron
2016, 116, 96.
1054; (d) Y. Y. Li, S. L. Yu, W. Y. Shen, J. X. Gao, Acc. Chem. Res. 2015,
48, 2587; (e) S. Chakraborty, P. Bhattacharya, H. Dai, H. Guan, Acc.
Chem. Res. 2015, 48, 1995.
[
16] (a) B. Maji, M. K. Barman, Synthesis 2017, 49, 3377; (b) M. Garbe, K.
Junge, M. Beller, Eur. J. Org. Chem. 2017, 2017, 4344; (c) J. R. Carney,
B. R. Dillon, S. P. Thomas, Eur. J. Org. Chem. 2016, 2016, 3912; (d) F.
Kallmeier, R. Kempe, Angew. Chem. Int. Ed. 2018, 57, 46; (e) D. A.
Valyaev, G. Lavigne, N. Lugan, Coord. Chem. Rev. 2016, 308, 191.
17] A. Mukherjee, A. Nerush, G. Leitus, L. J. Shimon, Y. Ben David, N. A.
Espinosa Jalapa, D. Milstein, J. Am. Chem. Soc. 2016, 138, 4298.
18] M. Anderez-Fernandez, L. K. Vogt, S. Fischer, W. Zhou, H. Jiao, M.
Garbe, S. Elangovan, K. Junge, H. Junge, R. Ludwig, M. Beller, Angew.
Chem. Int. Ed. 2017, 56, 559.
[31] K. Barta, P. C. Ford, Acc. Chem. Res. 2014, 47, 1503.
[32] F. G. Bordwell, Acc. Chem. Res. 1988, 21, 456.
[33] (a) B. Blank, R. Kempe, J. Am. Chem. Soc. 2010, 132, 924; (b) Y. Obora,
S. Ogawa, N. Yamamoto, J. Org. Chem. 2012, 77, 9429.
[
[
[34] T.-Y. Feng, H.-X. Li, D. J. Young, J.-P. Lang, J. Org. Chem. 2017, 82,
4113.
[35] C. Chaudhari, S. M. A. Hakim Siddiki, K.-i. Shimizu, Tetrahedron Lett.
2013, 54, 6490.
[
[
[
[
19] S. Chakraborty, U. Gellrich, Y. Diskin-Posner, G. Leitus, L. Avram, D.
Milstein, Angew. Chem. Int. Ed. 2017, 56, 4229.
[36] (a) M. R. Friedfeld, M. Shevlin, J. M. Hoyt, S. W. Krska, M. T. Tudge, P.
J. Chirik, Science 2013, 342, 1076.
20] D. H. Nguyen, X. Trivelli, F. Capet, J.-F. Paul, F. Dumeignil, R. M. Gauvin,
ACS Catal. 2017, 7, 2022.
[37] A. Togni, L. M. Venanzi, Angew. Chem. Int. Ed. 1994, 33, 497.
[38] D. A. Megger, K. Rosowski, C. Radunsky, J. Kosters, B. Sitek, J. Muller,
Dalton Trans. 2017, 46, 4759.
21] M. Mastalir, M. Glatz, N. Gorgas, B. Stöger, E. Pittenauer, G. Allmaier, L.
F. Veiros, K. Kirchner, Chem. Eur. J. 2016, 22, 12316.
[39] M. A Lipkowitz, and T. Navarra, (2001) The Encyclopedia of Allergies
(2nd ed.) Facts on File, New York, p. 178, ISBN 0-8160-4404-X.
[40] A. Nerush, M. Vogt, U. Gellrich, G. Leitus, Y. Ben-David, D. Milstein, J.
Am. Chem. Soc. 2016, 138, 6985.
22] M. Mastalir, M. Glatz, E. Pittenauer, G. Allmaier, K. Kirchner, J. Am.
Chem. Soc. 2016, 138, 15543.
[
[
23] N. Deibl, R. Kempe, Angew. Chem. Int. Ed. 2017, 56, 1663.
24] F. Kallmeier, B. Dudziec, T. Irrgang, R. Kempe, Angew. Chem. Int. Ed.
2017, 56, 7261.
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Entry for the Table of Contents (Please choose one layout)
Layout 2:
COMMUNICATION
Milan K. Barman, Satyadeep Waiba, and
Biplab Maji*
Page No. – Page No.
Manganese Catalyzed Direct
Olefination of Methylheteroarenes
with Primary Alcohols
Direct olefination! Manganese catalyzed acceptorless-dehydrogenative-coupling
of primary alcohols with methylheteroarenes yields the (E)-disubstituted styryl
derivatives in very high yields and selectivities.
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