Ruthenium(II)-catalyzed olefination: Via carbonyl reductive cross-coupling

Article abstract of DOI:10.1039/c7sc04207h

Natural availability of carbonyl groups offers reductive carbonyl coupling tremendous synthetic potential for efficient olefin synthesis, yet the catalytic carbonyl cross-coupling remains largely elusive. We report herein such a reaction, mediated by hydrazine under ruthenium(ii) catalysis. This method enables facile and selective cross-couplings of two unsymmetrical carbonyl compounds in either an intermolecular or intramolecular fashion. Moreover, this chemistry accommodates a variety of substrates, proceeds under mild reaction conditions with good functional group tolerance, and generates stoichiometric benign byproducts. Importantly, the coexistence of KO^tBu and bidentate phosphine dmpe is vital to this transformation.

Full text of DOI:10.1039/c7sc04207h

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Ruthenium(II)-catalyzed olefination via carbonyl reductive cross-
coupling†
Received 00th January 20xx,
Accepted 00th January 20xx
Wei Weia,b,‡, Xi-Jie Daia,‡, Haining Wanga, Chenchen Lia, Xiaobo Yanga, and Chao-Jun Lia,*
DOI: 10.1039/x0xx00000x
www.rsc.org/
Natural availability of carbonyl groups offers reductive carbonyl challenges endure: (1) stoichiometric quantities of metal
coupling tremendous synthetic potential for efficient olefin wastes accompanied by the excessive usage of metal-based
synthesis, yet the catalytic carbonyl cross-coupling remains largely reagents, and (2) poor chemoselectivity and functional group
elusive. We report herein such a reaction, mediated by hydrazine tolerance stemmed from the presence of strong metal
under ruthenium(II) catalysis. This method enables facile and reductants. As the synthetic community calls for more
selective cross-couplings of two unsymmetrical carbonyl sustainable and efficient chemical syntheses, carbonyl cross-
compounds in either an intermolecular or intramolecular fashion. coupling represents an ideal strategy to access olefins because
Moreover, this chemistry accommodates a variety of substrates, naturally prevailing carbonyl functionalities are generally
proceeds under mild reaction conditions with good functional regarded as renewable feedstocks.
group tolerance, and generates stoichiometric benign byproducts.
McMurry olefination: LVT-mediated carbonyl homo-coupling
Importantly, the coexistence of KOtBu and bidentate phosphine
[Ti]
R2
R2
O
R2
dmpe is vital to this transformation.
Ti(III) or Ti(IV)
R2
O
O
R1
R2
metal pinacolates
R1
(a)
+
+
O
Ti O
R1
metal reductants
R1
O
R1
R1
R2
Efficient construction of carbon–carbon double bonds has long
been a central pursuit in the synthetic community. Recent
decades have witnessed impressive accomplishments in the
field of carbonyl olefination.1-6 Well-known milestones include,
among others, the Wittig reaction,4 the Peterson reaction,5 the
Julia olefination6 and the Tebbe-Petasis olefination.7 Parallel to
these classical olefination methods, the McMurry reaction
mediated by low-valent titanium (LVT) reagents enables direct
reductive homo-couplings of carbonyl compounds for facile
synthesis of olefins (Scheme 1, a).8 Mechanistically, the
synergy between oxophilic titanium (III)/(IV) and strong metal
reductants (e.g. LiAIH4 and alkali metals) is crucial to form
metal pinacolates as key intermediates. One problematic
scenario pertaining to the original protocol, however, is that
the cross-coupling of two unsymmetrical carbonyl compounds
generally affords a statistic mixture of coupling products.8
Despite McMurry-type variants (e.g. external ligands and
auxiliaries) have been developed to bypass this issue,9 two
(E & Z)
• excess metal-based reagents & wastes
• poor functional group tolerance
Our approach: Ru(II)-catalyzed carbonyl cross-coupling
R3
O
R3
R2
R2
N2H4
R2
N
[Ru]
R4
cat. RuII
N
R3
R1
+
N2
+
H2O
(b)
R1
NH2
O
R4
R1
O
R1
N
R2
R4
(E & Z)
chair-like metallacycle
• catalytic metal & benign byproducts
• good functional group tolerance
Scheme 1 Olefination methods via reductive carbonyl coupling.
Very recently, we have disclosed a ruthenium-catalyzed
deoxygenation reaction for the highly selective cleavage of
aliphatic primary C-O bonds.10 Building on the similar
ruthenium(II) catalysis, we further demonstrated its
robustness in catalyzing a series of new carbon-carbon bond
forming processes through addition reactions to various
carbonyl compounds, imines and activated alkenes.11-13
Variations of these precedents notwithstanding, one of their
commonalities is to use aldehydes/ketones as alkyl carbanion
equivalents via hydrazone formation. As a continuation of our
interests in utilizing such carbanion equivalents for useful
synthetic transformations, we describe herein the
development of a ruthenium(II)-catalyzed, hydrazine-mediated
olefination reaction via carbonyl reductive cross-coupling
(Scheme 1, b). This catalytic method features good functional
group tolerance and generates nitrogen and water as the only
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environmentally benign byproducts in stoichiometric parameters such as solvent, additive and temperature play minor
quantities.14,15
roles in the current reaction, the following observations are worthy
Table 1 Optimization of reaction conditionsa
Table 2 Scope of electrophilic carbonyl coupling partnersa,b
2
[Ru(p-cymene)Cl2]2(1.5 mol%)
R3
O
O
N2H4 H2O
dmpe (3 mol%)
NH2
R3 R4
R4
KOtBu (50 mol%), CsF(75 mol%)
N
THF, r.t., 30 min
H
2
3
THF, 45 oC,12 h, N2
1a
F
F
F
PhO
OPh
3b 71%c
3c 78%
3a 79%
3d 71%
Cl
Cl
Cl
3e 78%
(E/Z: 50/50)
3f 80%
(E/Z: 52/48)
Cl
Cl
3g 72%
(E/Z: 50/50)
3h 74%
(E/Z: 55/45)
3i 78%
(E/Z: 65/35)
X
3ia X= 4-OMe, 73%, (E/Z: 65/35)
3ib X= 3-OMe, 78%, (E/Z: 67/33)
3k 75% (E/Z: 60/40)
3j 65%(E/Z: 57/43)
3ic X= 4-OPh, 75% (E/Z: 64/36)
3id X= 4-Ph, 80% (E/Z: 65/35)
3ie X= 4-Cl, 72% (E/Z: 64/36)
3if X= 4-Br, 70% (E/Z: 62/38)
3ig X= 2-F, 68% (E/Z: 68/32)
a
1a (0.28 mmol, 1.4 equiv.), N2H4·H2O (0.3 mmol, 1.5 equiv.), THF
(0.14 mL), rt, 30 min; 2a (0.20 mmol, 1.0 equiv.), [Ru(p-cymene)Cl2]2
(0.003 mmol, 1.5 mol%), ligand (0.006 mmol, 3.0 mol%), base (0.1
mmol, 50 mol%), additive: CsF (0.15 mmol, 75 mol%), 45oC, 12 h,
3m 26% (E/Z> 99:1)
3l 77% (E/Z: 58/42)
3ih X= 2-F, 4-OMe, 70% (E/Z: 66/34)
under N2. b Yields were determined by crude 1H NMR usin
as an internal standard. c Without [Ru(p-cymene)Cl2]2.
g mesitylene
3ii X= 4-SMe, 71% (E/Z: 64/36)
Me
, 40% (E/Z: 64/36)
OH
3ij X=
4-
Me
Me
H
, 50% (E/Z: 69/31)
3ik X=4- OMe
Initially, propionaldehyde 1a and benzophenone 2a were used as
carbonyl partners in our investigation. By varying the reaction
conditions employed in carbonyl addition,11 we detected the
corresponding olefin 3a in 51% yield from the cross-coupling
between preformed hydrazone of 1a and 2a after 12 h (Table 1,
entry 1). In line with our basicity rationale, a variety of bases were
prioritized in the optimization process. In fact, improved yields were
consistently observed using stronger inorganic bases such as
hydroxides and alkoxides, among which KOtBu gave the best result
(Table 1, entries 1-5; Table S3, ESI†). In contrast, organic base (e.g.
Et3N) and weaker inorganic base (e.g. K2CO3) were significantly
inferior (Table 1, entries 6 and 7). Moreover, the amount of base
matters significantly for this reaction. Specifically, lower loadings
than substoichiometric quantity (i.e. 50 mol%) were associated with
yield attenuation (Table S4, ESI†). As expected, the olefination
reaction did not proceed in the absence of base (Table 1, entry 8).
In addition to the basicity, both ruthenium (II) pre-catalyst and
bidentate phosphine ligand 1,2-bis(dimethylphosphino)ethane
(dmpe) are essential for the elimination to occur. Likewise, no
desired product was obtained without either one of them (Table 1,
entries 9 and 10). Subsequent screenings on various ruthenium
catalysts (Table S1, ESI†) and phosphine ligands (Table 1, entries 11-
14; Table S2, ESI†)16 revealed that the combination of [Ru(p-
cymene)Cl2]2 and dmpe provided the biggest catalytic turnover
number, and thus the highest yield. Although other reaction
H
H
H
3il X=
4- N
4-
, 53% (E/Z: 65/35)
H
3ne 26% (21%)
3oe 27% (66%)
3im X=
Ph, 67% (E/Z: 66/34)
3in X= 4-CO2Me, 50% (E/Z: 73/27)d
O
3io X= 4-
3ip X= 4-
, 66% (E/Z: 69/31)d
, 60% (E/Z: 66/34)d
C
N
O
C
NHBu
a
1a (0.28 mmol, 1.4 equiv.), N2H4·H2O (0.3 mmol, 1.5 equiv.), THF
(0.14 mL), rt, 30 min; 2 (0.20 mmol, 1.0 equiv.), [Ru(p-cymene)Cl2]2
(0.003 mmol, 1.5 mol%), dmpe (0.006 mmol, 3.0 mol%), KOtBu (0.1
mmol, 50 mol%), CsF (0.15 mmol, 75 mol%), 45oC, 12 h, under N2.
Isolated yields and the ratio of E/Z isomers were determined by crude
b
1H NMR analysis. c 80oC. K3PO4 (0.1 mmol, 50 mol%), 12 h. e Yields
d
were determined by crude 1H NMR using mesitylene as an internal
standard. Yields of asymmetric azines were given in the parentheses.
noting. For example, ether solvents (e.g. THF, 1,4-dioxane, 1,2-
dimethoxyethane) favor the olefination over other types of solvents
(Table S5, ESI†). Addition of cesium fluoride as an additive slightly
increases the reaction yield (Table S6, ESI†).
With the standard reaction conditions in hand, we moved on to
study the scope of electrophilic carbonyl partners (Table 2). In
general, this chemistry covers a broad spectrum of benzophenone
and its derivatives, regardless of their electronic nature.
Consequently, the corresponding olefins (3a-h) were obtained in
moderate to good yields. For unsymmetrical benzophenones, a
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mixture of stereoisomers (E/Z isomers) was produced (3e-h). with other aromatic aldehydes typically proceeded well to yield
Similarly, acetophenones bearing a wide range of aryl substituents
Table 3 Scope of nucleophilic carbonyl coupling partnersa,b
various stilbenes with excellent stereoselectivity (4h-k). In the latter
cases, using K2CO3 as the base at elevated temperature was
necessary. Encouragingly, more sterically demanding aromatic
ketones (i.e. acetophenone) worked as nucleophilic partner,
providing 4l in moderate yield with high stereoselectivity. Finally,
the intramolecular olefination was evaluated with 3-(2-
benzoylphenyl)propanal 1m and 6-oxo-6-phenylhexanal 1n. The
corresponding cyclohexene derivatives 4m and 4n were obtained in
51% and 48% yields, respectively.
Mechanistically, two scenarios are possible to form olefins.
One is metal-assisted decomposition of the corresponding
asymmetric azine. The other is base-mediated elimination of
the corresponding alcohol. In other words, both asymmetric
azines and alcohols might have been generated prior to olefins.
To exclude these possibility, two parallel control experiments
were conducted with the presynthesized azine 6i and 1,1-
diphenylbutan-1-ol 5a under standard conditions, respectively
(Scheme 2). However, olefin products (3i and 3a) were not
detected in both cases. The above results strongly suggested
that olefins were eliminated from a transient intermediate,
rather than azines or alcohols, via a E1cB-type mechanism.
a 1 (0.28 mmol, 1.4 equiv.), N2H4
·H2O (0.3 mmol, 1.5 equiv.), THF (0.14
mL), rt, 30 min; 2 (0.20 mmol, 1.0 equiv.), [Ru(p-cymene)Cl2]2 (0.003
mmol, 1.5 mol%), dmpe (0.006 mmol, 3.0 mol%), KOtBu (0.1 mmol, 50
b
mol%), CsF (0.15 mmol, 75 mol%), 45oC, 12 h, under N2. Isolated
yields and the ratio of E/Z isomers were determined by crude H NMR
1
d
analysis. c 60 oC, 24h. [(C6Me6)RuCl2]2 (0.003 mmol, 1.5 mol%) was
used as catalyst. e K2CO3 (0.1 mmol, 50 mol%), 120 oC, 24 h.
Scheme 2 Control experiments for the olefin formation.
were surveyed, with the formation of E/Z isomers (E-isomer
predominant) in moderate to good yields (3i-ip). Notably, functional
groups that are commonly incompatible with traditional carbonyl
olefination approach such as unprotected alcohol, ester and amide
groups, were well tolerated in this chemistry and thus amenable to
further functionalization (3ij, 3in and 3ip). Intriguingly, aromatic
ketones substituted by linear alkyl chains (2-5 carbons) did not
hamper the reaction leading to the desired products in good yields
(3j-l). Aromatic aldehyde and aliphatic ketones can also serve as
coupling partners, including the relatively complex oxo-steroid
compound. Asymmetric azines were observed as major products
with cyclic aliphatic ketones (3o). However, the complex reaction
mixture was resulted in the case of acyclic aliphatic ketone (3n),
whereby the corresponding asymmetric azine was obtained as one
of the major side products. Low yields were therefore seen in all
these substrates at this stage.
Based on all experimental data, the preliminary
computational calculations done on the previous carbonyl
addition chemistry11 and studies from others,14 a postulated
reaction pathway was proposed as shown in Scheme 3. The
bidentate phosphine coordinated complex
I is initially
generated by a ligand dissociation/association between [Ru(p-
cymene)Cl2]2 and dmpe, followed by a ligand association with
carbonyl-derived hydrazone
B and carbonyl C in the presence
of KOtBu, giving rise to complex II and III respectively.
Formation of the coordinately intermediate III sets the stage
for the intramolecular isomerization. This concerted process
yields the key six-membered ring intermediate IV by forming a
new carbon-carbon bond between
A . Base-catalyzed
and C 14
decomposition of diimide intermediate IV via a E1cB-type
mechanism produces the desired olefins along with the
Subsequently, the scope of nucleophilic carbonyl coupling
partners was tested (Table 3). Linear saturated aliphatic aldehydes,
irrespective of carbon chain length, all delivered the corresponding
olefins in moderate to good yields (4a-f). Although aromatic
aldehydes were poorly coupled with aromatic ketones (i.e. The
reductive coupling of benzaldehyde with benzophenone leading to
product 4g) due to competing alcohol formation, their couplings
formation of ruthenium hydroxide species
cycle, then reacts with hydrazone to release water and
active species II (X = Cl). Alternatively, the chloride anionic
ligand on could have been replaced by , leaving hydroxide
V. To turnover the
V
B
V
B
on the active species VI (X = OH) and other ruthenium
complexes (III-V).
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3
(a) W. S. Wadsworth and Jr. W. D. Emmons, J. Am. Chem. Soc.,
1961, 83, 1733–1738; (b) C. R. Johnson, J. R. Shanklin and R. A.
Kirchhoff, J. Am. Chem. Soc., 1973, 95, 6462–6463; (c) S. Sano, T.
Takehisa, S. Ogawa, K. Yokoyama and Y. Nagao, Chem. Pharm.
Bull. 2002, 50, 1300–1302; (d) Z-Y. Peng, F-F. Ma, L-F. Zhu, X-M.
Xie and Z. Zhang, J. Org. Chem. 2009, 74, 6855−6858.
4 (a) G. Wittig and G. Geissler, Liebigs Ann. Chem. 1953, 580, 44–57;
(b) G. Wittig and U. Schollkopf, Ber. Dtsch. Chem. Ges. 1954, 87
1318–1330; (c) J. Boutagy and R. Thomas, Chem. Rev. 1974, 74
87–99; (d) B. E. Maryanoff and A. B. Reitz, Chem. Rev. 1989, 89
863–927.
,
,
,
5 (a) D. J. Peterson, J. Org. Chem., 1968, 33, 780–784; (b) J. Huang,
C. Wu and W. D. Wulff, J. Am. Chem. Soc. 2007, 129, 13366–
13367; (c) D. J. Ager, The Peterson Olefination Reaction, L. A.
Paquette, Ed. Organic Reactions, 1990, 38, 1-224.
6 (a) M. Julia and J. M. Paris, Tetrahedron Lett 1973, 14, 4833–4836;
(b) P. R. Blakemore, J. Chem. Soc., Perkin Trans. 1 2002, 2563–
2585; (c) K. Ando, T. Kobayashi and N. Uchida, Org. Lett. 2015,
17, 2554−2557.
7 (a) F. N. Tebbe, G. W. Parshall and G. S. Reddy, J. Am. Chem.
Soc. 1978, 100, 3611–3613; (b) I. Beadham and J. Micklefield,
Curr. Org. Syn. 2005, 2, 231–250; (c) N. A. Petasis and E. I. Bzowej,
J. Am. Chem. Soc. 1990, 112, 6392–6394.
Scheme 3 Possible reaction mechanism.
8 (a) J. E. McMurry and M. P. Fleming, J. Am. Chem. Soc., 1974, 96
,
4708–4709; (b) J. E. McMurry and L. R. Krepski, J. Org. Chem.
1976, 41, 896–897; (c) S. Tyrlik and I. Wolochowicz, Bull. Soc.
Chim. Fr. 1973, 2147-2148; (d) B. E. Kahn and R. D. Rieke, Chem.
Conclusions
Rev. 1988, 88, 733–745; (e) J. E. McMurrv. Chem. Rev. 1989, 89
,
In summary, we have developed an ruthenium(II)-catalyzed,
hydrazine-mediated olefination method via reductive carbonyl
1513–1524; (f) T. Takeda and A. Tsubouchi, The McMurry
Coupling and Related Reactions, S. E. Denmark, Ed.; Organic
Reactions, 2013, 82, 1-470.
coupling reactions. This chemistry possesses
a distinct
mechanistic profile and highlights the use of naturally
abundant carbonyl functionalities for efficient olefin synthesis.
Other striking features include cross-coupling capability, mild
reaction conditions, good functional group tolerance and
stoichiometric benign byproducts. Taken together, our findings
are expected to spur more interests in developing catalytic
methods in this field. Further investigations on increasing the
reaction scope, synthetic applications and mechanistic details
are undergoing in our laboratory.
9
(a) N. Balu, S. K. Nayak and A. Banerji, J. Am. Chem. Soc. 1996,
118, 5932–5937; (b) C. Villiers and M. Ephritikhine, Chem. Eur. J.
2001, 7, 3043–3051; (c) M. H. Chisholm and J. A. Klang, J. Am.
Chem. Soc. 1989, 111, 2324–2325; (d) X-F. Duan, J. Zeng, J-W. Lü
and Z-B. Zhang, J. Org. Chem. 2006, 71, 9873–9876; (e) H. R.
Diéguez, A. López, V. Domingo, J. F. Arteaga, J. A. Dobado, M.
Mar Herrador, J. F. Quílez del Moral and A. F. Barrero, J. Am.
Chem. Soc. 2010, 132, 254–259; (f) L. Zhang, X. Yu, L. Zhang, X.
Zhou and Y. Lin, Org. Chem. Front. 2014,
10 X-.J. Dai and C.-J. Li, J. Am. Chem. Soc. 2016, 138, 5433−5440.
11 H. Wang, X-.J. Dai and C.-J. Li, Nat. Chem. 2016, , 374−378.
12 N. Chen, X-J. Dai, H. Wang and C-J. Li, Angew. Chem., Int. Ed.,
2017, 56, 6260-6263.
1, 929-935.
9
This work was financially supported by the Canada Research
Chair (Tier 1) foundation, FQRNT (CCVC), NSERC, CFI and
McGill University. We also thank the CSC (China Scholarship
Council) for the postdoctoral fellowship (W. Wei).
13 X-J. Dai, H. Wang and C-J. Li, Angew. Chem., Int. Ed., 2017, 56
6302-6306.
,
14 A few examples for the formation of carbon-carbon double bond
via the coupling of stoichiometric metalloazines with carbonyl
compounds, see: (a) G. M. Arvanitis, J. Schwartz and D. Van
References
Engen, Organometallics 1986,
Meier and J. Schwartz, J. Am. Chem. Soc. 1986, 108, 1322–1323;
(c) G. M. Arvanitis and J. Schwartz, Organometallics 1987, , 421–
423; (d) G. M. Arvanitis, J. Smegal, I. Meier, A. C. C. Wong, J.
Schwartz and D. Van Engen, Organometallics 1989, , 2717–2723.
15 A recent review on ruthenium-catalyzed transfer hydrogenation
for C–C bond formation, see: F. Perez, S. Oda, L.M. Geary and M.
J. Krische, Top. Curr. Chem. 2016, 374, 365-387.
5, 2157–2159; (b) J. A. Smegal, I. K.
1 (a) S. E. Kelly, In Alkene Synthesis; B. M. Trost and I. Fleming, Eds.;
Comprehensive Organic Synthesis; Pergamon Press: Oxford, 1991;
Vol. 1, p 729–817; (b) D. M. Hodgson and L. T. Boulton, In
Preparation of Alkenes; J. M. J. Williams, Ed.; Oxford University
Press: Oxford, 1996; p 81; (c) R. Dumeunier and I. E. Markó, In
Modern Carbonyl Olefination; T. Takeda, Ed.; Wiley-VCH:
Weinheim, Germany, 2004.
6
8
2 (a) A. H. Hoveyda and A. R. Zhugralin, Nature. 2007, 450, 243–251;
16 For the reactions of [RuCl2(ƞ6-arene)]2 with tertiary phosphines,
please see. (a) R. A. Zelonka and M. C. Baird, Can J. Chem.,
1972, 50, 3063-3072; (b) M. A. Bennett and A. K. Smith J. Chem.
Soc., Dalton Trans. 1974, 233-241; (c) H. Werner, R. Werner,
Chem. Ber., 1982, 115, 3766-3780; (d) M. A. Bennett, T.-N.
(b) X. Guo, J. Wang and C.-J. Li, J. Am. Chem. Soc, 2009, 131
,
15092–15093; (c) S. Takemoto, E. Shibata, M. Nakajima, Y.
Yumoto, M. Shimamoto and H. Matsuzaka, J. Am. Chem. Soc.
2016, 138, 14836–14839; (d) J. R. Ludwig, P. M. Zimmerman, J. B.
Gianino and C. S. Schindler, Nature. 2016, 533, 374–379.
4 | J. Name., 2012, 00, 1-3
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Huang, J. L. Latten, J. Organomet. Chem., 1984, 272, 189-205;
(e) M. A. Bennett, J. L. Latten, Aust. J. Chem., 1987, 40, 841-849.
(f) P. Pertici, S. Bertozzi, R. Lazzaroni, G. Vitulli, M. A. Bennett, J.
Organomet. Chem., 1988, 354, 117-121.
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A catalytic olefination method via carbonyl reductive cross-coupling was achieved by
ruthenium (II) catalysis.