A convenient and general reduction of amides to amines with low-valent titanium

Article abstract of DOI:10.1002/adsc.201300355

Low-valent titanium readily prepared in situ from TiCl₄ and Mg powder in THF is found to be an active agent for the reduction of amides which were previously considered to be inert towards low-valent titanium. The reaction proceeds under very mild conditions, and is applicable to all types of amides, primary, secondary and tertiary, to produce the corresponding amines in good to excellent yields. This new finding provides a practical, convenient and general method for the important transformation of amides to amines. A plausible reaction mechanism is proposed.

Full text of DOI:10.1002/adsc.201300355

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DOI: 10.1002/adsc.201300355
A Convenient and General Reduction of Amides to Amines with
Low-Valent Titanium
Tongxin Zhang,a Yan Zhang,a Weixi Zhang,a and Meiming Luoa,*
a
Key Laboratory of Green Chemistry & Technology of Ministry of Education, College of Chemistry, Sichuan University,
Chengdu 610064, Peopleꢀs Republic of China
Fax : (+86)-28-8546-2021; phone: (+86)-28-8546-2021; e-mail: luomm@scu.edu.cn
Received: April 26, 2013; Revised: July 16, 2013; Published online: && &&, 0000
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201300355.
Abstract: Low-valent titanium readily prepared in
situ from TiCl4 and Mg powder in THF is found to
be an active agent for the reduction of amides
which were previously considered to be inert to-
wards low-valent titanium. The reaction proceeds
under very mild conditions, and is applicable to all
types of amides, primary, secondary and tertiary, to
produce the corresponding amines in good to excel-
lent yields. This new finding provides a practical,
convenient and general method for the important
transformation of amides to amines. A plausible re-
action mechanism is proposed.
es (Scheme 1, method b).[4,5] While the reliability of
these reagents has been amply demonstrated, still re-
maining challenges include side reactions such as
[4s]
À
C N bond cleavage with hindered tertiary amides,
bond cleavage with formation of aldehydes or alco-
hols in some cases,[4d] difficulties often encountered in
the isolation of product from the reaction mixture
with the reducing agents due to the formation of com-
plexes with the resultant amines.[4e,i,p] Recently, break-
throughs were reported in metal-free reductions of
tertiary and secondary amides with high chemoselec-
tivity using expensive reagents (triflic anhydride as
the activating reagent and both triethylsilane and
Hantzsch ester as hydride source) (Scheme 1, method
c).[6] Thus, the development of mild and general re-
duction methods applicable to amides of all types, ter-
tiary, secondary and primary is still desirable.
Keywords: amides; amines; low-valent titanium;
magnesium; reduction
Low-valent titanium reagents have been well-
known as powerful electron donors to accomplish cer-
The reduction of amides to amines is a fundamental
transformation in organic chemistry for the synthesis
of amines which constitute an important class of com-
pounds in chemistry, biology and materials.[1] The re-
duction of amides to amines can be effected either
chemically with stoichiometric amounts of reducing
agents or by transition metal-catalyzed hydrogena-
tion. Obviously, catalytic hydrogenation (Scheme 1,
method a) using molecular hydrogen represents the
ideal method for the reduction of amides to amines,
but the reaction is still in the initial stage and requires
vigorous conditions.[2] Complementary to hydrogena-
tion with molecular hydrogen, various transition
metal-catalyzed
organosilane
reductions
have
emerged as attractive alternatives for the conversion
of different types of amides to amines in the last
decade (Scheme 1, method a).[3] On the other hand,
chemical reductions of amides to amines using stoi-
chiometric amounts of reducing agents are most
widely used, often traditional aluminum and boron
hydride-mediated reductions prevail for such process- Scheme 1. Methods for the reduction of amides to amines.
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Table 1. Reduction of N-phenylbenzamide with Mg/TiCl4.[a]
tain deoxygenation reactions such as reductive cou-
pling of carbonyl compounds, reduction of sulfoxides,
epoxides, N-nitrosoamines, bromohydrins, and cyano-
hydrins.[7] Amides are, however, considered to be
inert towards low-valent titanium reagents.[7a,c,8] As far
as we know, only a few amides with specific structures
react with low-valent titanium reagents. Acylamido-
carbonyl componds in the presence of low-valent tita-
nium reagents underwent intramolecular ketone–
amide coupling providing a remarkably efficient entry
to pyrrole and indole derivatives.[7c,8] Phthalimide was
converted to phthalimidine by the low-valent titanium
reagent prepared from Zn and TiCl4 in xylene after
heating for 20 h at 1108C,[9] but the reaction could not
be extended to other amides. Despite the limited suc- Entry
Solvent
Amide:TiCl4:Mg[b]
Yield [%][c]
cesses in deoxygenation of specific amides, the strong
oxophilic nature of titanium and the significance of
the reduction of amides to amines still encouraged us
3
1
2
THF
THF
THF
THF
THF
Et2O
DME
1,4-dioxane
toluene
1:3:6
1:4:8
1:5:10
1:5:5
1:6:12
1:5:10
1:5:10
1:5:10
1:5:10
60
72
93
30
to explore the potential of using low-valent titanium
as a mild, cost-effective and general agent for the re-
duction of amides to amines (Scheme 1, method d).
A number of agents can reduce TiCl4 to low-valent
titanium, including LiAlH4, alkaline metal, Zn and
Mg powder.[7] For simplicity and convenience, our at-
tention turned to Zn and Mg powders. Since low-
valent titanium prepared from Zn and TiCl3 in THF
has already been proved to be incapable of reducing
N-phenylbenzamide,[8] Mg powder was finally em-
ployed for the preparation of a low-valent titanium
reagent from TiCl4 in this study. Initially, the reduc-
4
5
6
7
8
9
90
no reaction
no reaction
no reaction
no reaction
[a]
Reaction conditions: 1a (1 mmol), Mg, TiCl4, solvent
(60 mL), Ar, room temperature, 4 h.
Molar ratio.
[b]
[c]
Isolated yield.
tion of N-phenylbenzamide with Mg/TiCl4 was investi- tries 6–9). Thus the optimized reaction conditions in-
gated as a model system to identify and optimize the volved use of an amide/TiCl4/Mg molar ratio of 1:5:10
reaction parameters (Table 1). The reduction was per- in THF at ambient temperature.
formed at room temperature by adding the THF solu-
Having identified the optimized reaction conditions,
tion of N-phenylbenzamide to the low-valent titanium we then explored the scope and limitations of the re-
suspension which was prepared in situ by addition of duction of amides to amines with low-valent titanium
TiCl4 to an ice-cooled THF solution containing Mg reagent. Satisfactorily as shown in Table 2, this reduc-
powder. To our delight, when the reaction was carried tion is applicable not only to secondary (Table 2, en-
out with an amide/TiCl4/Mg molar ratio of 1:3:6, N- tries 1–19), but also to tertiary (Table 2, entries 20–32)
phenylbenzamide (1a) was converted to N-benzylani- and primary amides (Table 2, entries 33–36). Aromat-
line (2a) in 60% yield with some 1a remaining uncon- ic, aliphatic, and heterocyclic amides were reduced
sumed (Table 1, entry 1). It was found that the molar smoothly to the corresponding amines in good to ex-
ratio of amide/TiCl4/Mg affected the reaction yield cellent yields. Common functional groups including
significantly. When the molar ratio of 1a/TiCl4/Mg methoxy (Table 2, entries 3, 21 and 35), halide
was increased to 1:5:10, the reaction was complete (Table 2, entries 5, 6, 8, 22 and 34), amino (Table 2,
within 4 h affording amine 2a in 93% yield (Table 1, entries 4 and 23), hydroxy (Table 2, entries 10 and
entry 3). While less amounts of TiCl4 and/or Mg led 24), benzyl (Table 2, entries 11 and 32), and tert-butyl
to incomplete conversion and lower product yield carbamate [Eq. (1)] were all compatible with the re-
(Table 1, entries 1, 2 and 4), increasing the amount of action conditions. In agreement with the reported re-
TiCl4 and Mg to an amide/TiCl4/Mg ratio of 1:6:12 did sults,[11] a nitro group was reduced to an amino group
not improve the amine yield further (Table 1, (Table 2, entry 7). Notably, concomitant reductions of
entry 5). As many other low-valent titanium-mediated ester group on an arene to methyl rather than
reactions,[7–10] it was found that the solvent was critical hydroxy
ACTHNUTRGNEUmGN ethyl (entries 9 and 25) and alkene to
to the present reduction which took place only in alkane (entry 12) are not readily achieved by other
THF. In other tested solvents such as diethyl ether, methods, and may find application in some multistep
1,2-dimethoxyethane (DME), 1,4-dioxane and tolu- synthesis.[5c,i] Although secondary and tertiary amides
ene, the reaction did not occur at all (Table 1, en- were reduced at room temperature, the reduction of
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A Convenient and General Reduction of Amides to Amines with Low-Valent Titanium
Table 2. Reduction of various amides with Mg/TiCl4 in THF.[a]
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Table 2. (Continued)
[a]
Reaction conditions: amide (1 mmol), Mg (10 mmol), TiCl4 (5 mmol), THF (60 mL), Ar, room tempera-
ture.
[b] Isolated yield.
[c]
Amide/TiCl4/Mg=1:10:20.
[d] The reduction was conducted at 08C.
primary amides and lactam was best conducted at processes troublesome. One report identified the
08C (Table 2, entries 19, 33–36). For example, while structure of this low-valent titanium reagent as
the reduction of lactam 1s proceeded cleanly at 08C [TiMgCl2·xTHF] or [TiACHTNUGTRNEUNG(MgCl)2·xTHF] depending on
within 2 h to give amine 2s in 82% yield, complex the stoichiometry,[12] others observed that adsorbed/
À
products were generated according to TLC monitor- chemisorbed hydrogen atoms and Ti H bond were
ing when the reaction was carried out at room tem- present in the low-valent titanium reagent.[10,11] The
perature. The reduction can also be applied to enan- adsorbed/chemisorbed hydrogen atoms are consid-
tioenriched amides: chiral amides (S)-3k of 98.5% ee ered as being abstracted from THF with formation of
and (R)-3k of 99.1% ee were reduced under the opti- furan. Thus, the low-valent titanium reagent prepared
mized conditions to chiral amines (S)-4k in 81% yield from Mg and TiCl4 in THF may be designated as [Ti]
and 98.9% ee, and (R)-4k in 83% yield and 99.9% ee [H]. To address where the hydrogen atoms came from
respectively, showing that no racemization took place in the reduction of amides to amines, low-valent tita-
[Eq. (1)].
nium [Ti][D] prepared from Mg and TiCl4 in THF-d8
Although the low-valent titanium reagent prepared was employed to reduce phenyl(piperin-1-yl)methan-
from Mg and titanium chloride in THF has been used
ACHTUNGTRENoNGNU ne 1t [Eq. (2)]. After treating the post-reaction mix-
for a wide range of reactions,[7,10,11] the actual structure ture with H2O, we obtained N-benzylpiperidine 2t, to-
is unknown, making interpretation of the reaction gether with deuteriated products 2t-d1 and 2t-d2 in
molar ratio of 58:35:7 [Eq. (2)]. This result suggests
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A Convenient and General Reduction of Amides to Amines with Low-Valent Titanium
added. The reaction was continued at room temperature
until the amide was completely converted as shown by TLC
monitoring. The reaction mixture was then cooled in an ice-
bath and basified to pH >9 with saturated NaHCO3 and
aqueous NaOH (20%) solution. The resulting mixture was
filtered, and the filtrate was extracted with CH2Cl2 repeated-
ly. The extracts were washed with brine, dried over anhy-
drous Na2SO4 and evaporated. The residue was purified by
column chromatography on silica gel using ethyl acetate/pe-
troleum ether/triethylamine (1%) to afford the pure prod-
uct. The reactions are strongly exothermic at high concen-
trations. When the reactions are performed at higher con-
centrations, cooling is required for the entire process to
keep the reaction system at room temperature.
Scheme 2. Proposed reaction mechanism.
that a titanium carbene intermediate 6 likely be in-
volved (Scheme 2). Carbenoid species were proposed
as intermediates previously in the reaction of sterical-
ly hindered ketones with low-valent titanium re-
agents.[13] Hydrolysis of 6 would produce non-deuteri-
ated amine 7. Intermediate 6 would also be trans-
formed to amine 9 with two deuterium atoms, via an
alkyl intermediate 8, by successive addition of deute-
rium atoms from [Ti][D]. Hydrolysis of 8 would gen-
erate amine 10 with one deuterium atom. Reduction
of alkene to alkane (Table 2, entry 12) could be most
likely attributed to the adsorbed/chemisorbed hydro-
gen atoms on low-valent titanium. When 1t was re-
duced with [Ti][H] and the post-reaction mixture was
treated with D2O, 2t, 2t-d1 and 2t-d2 were obtained in
molar ratio of 25:44:31, which further supports the
proposed mechanism.
Acknowledgements
We thank the Natural Science Foundation of China for finan-
cial support (21021001, 21072134 and J1103315/J0104) and
the Analytical & Testing Centre of Sichuan University for
NMR and MS measurements.
References
[1] a) Comprehensive Organic Synthesis, Vol. 8, (Eds.:
B. M. Trost, I. Fleming), Pergamon: Oxford, 1991;
b) Comprehensive Organic Transformations: A Guide
to Functional Group Preparations, 2nd edn., (Ed.: R. C.
Larock), Wiley-VCH, New York, 1999; c) M. A. Ricci,
Modern Amination Methods, Wiley, New York, 2000;
d) Modern Reduction Methods, (Eds.: P. G. Anderson,
I. J. Munslow), Wiley, New York, 2008.
In summary, we have disclosed that low-valent tita-
nium prepared in situ from TiCl4 and Mg powder in
THF can be used to reduce amides which were previ-
ously considered to be inert towards low-valent tita-
nium.[7a,c,8] The reaction proceeds under very mild
conditions, and is applicable to all types of amides,
primary, secondary and tertiary, to produce the corre-
sponding amines in good to excellent yields. The con-
comitant reductions of ester group on an arene to
methyl and alkene to alkane are noteworthy. This
new finding provides a practical, convenient and gen-
eral method for the reduction of amides to amines,
and shows potential application in organic synthesis.
[2] a) J. G. de Vries, C. J. Elsevier, Handbook of Homoge-
neous Hydrogenation, Wiley-VCH, Weiheim, 2007;
b) A. A. NfflÇez, Magro, G. R. Eastham, D. J. Cole-
Hamilton, Chem. Commun. 2007, 3154; c) M. Stein, B.
Breit, Angew. Chem. 2013, 125, 2287; Angew. Chem.
Int. Ed. 2013, 52, 2231.
[3] a) R. Kuwano, M. Takahashi, Y. Ito, Tetrahedron Lett.
1998, 39, 1017; b) K. Selvakumar, J. F. Harrod, Angew.
Chem. 2001, 113, 2187; Angew. Chem. Int. Ed. 2001, 40,
2129; c) M. Igarashi, T. Fuchikami, Tetrahedron Lett.
2001, 42, 1945; d) K. Selvakumar, K. Rangareddy, J. F.
Harrold, Can. J. Chem. 2004, 82, 1244; e) T. Ohta, M.
Kamiya, M. Nobumoto, K. Kusui, I. Furukawa, Bull.
Chem. Soc. Jpn. 2005, 78, 1856; f) Y. Motoyama, K.
Mitsui, T. Ishihda, H. Nagashima, J. Am. Chem. Soc.
2005, 127, 13150; g) S. Hanada, T. Ishida, Y. Motoyama,
H. Nagashima, J. Org. Chem. 2007, 72, 7551; h) C. A.
Fernandes, C. C. Romao, J. Mol. Catal. A: Chem. 2007,
272, 60; i) N. Sakai, K. Fuhji, T. Konakahara, Tetrahe-
dron Lett. 2008, 49, 6873; j) S. Hanada, E. Tsutsumi, Y.
Motoyama, H. Nagashima, J. Am. Chem. Soc. 2009,
131, 15032; k) S. Zhou, K. Junge, D. Addis, S. Das, M.
Beller, Angew. Chem. 2009, 121, 9671; Angew. Chem.
Int. Ed. 2009, 48, 9507; l) Y. Sunada, H. Kawakami, T.
Imaoka, Y. Motoyama, H. Nagashima, Angew. Chem.
2009, 121, 9675; Angew. Chem. Int. Ed. 2009, 48, 9511;
m) S. Das, D. Addis, S. Zhou, K. Junge, M. Beller, J.
Experimental Section
General Procedure for the Reduction of Amides to
Amines
TiCl4 (0.54 mL, 5 mmol) was added to an ice-cooled THF
(60 mL) solution containing Mg powder (0.24 g, 10 mmol)
under an argon atmosphere. Upon addition of TiCl4, yellow
precipitates were produced. The mixture was stirred for 2 h
at room temperature to give a black suspension, to which
a solution of amide (1 mmol) in THF (15 mL) was slowly
Adv. Synth. Catal. 0000, 000, 0 – 0
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ÞÞ
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Tongxin Zhang et al.
COMMUNICATIONS
Am. Chem. Soc. 2010, 132, 1770; n) S. Das, D. Addis,
K. Junge, M. Beller, Chem. Eur. J. 2011, 17, 12186;
o) S. Park, M. Brookhart, J. Am. Chem. Soc. 2012, 134,
640; p) C. Cheng, M. Brookhart, J. Am. Chem. Soc.
2012, 134, 11304; q) S. Das, B. Join, K. Junge, M.
Beller, Chem. Commun. 2012, 48, 2683; r) J. T. Reeves,
Z. Tan, M. A. Marsini, Z. S. Han, Y. Xu, D. C. Reeves,
H. Lee, B. Z. Lu, C. H. Senanayake, Adv. Synth. Catal.
2013, 355, 47.
Bunt, R. C. Lemoine, T. L. Calkins, J. Am. Chem. Soc.
2000, 122, 5968; d) T. B. Smith, A. J. Wendt, J. AubØ,
Org. Lett. 2002, 4, 2577; e) T. Nagata, M. Nakagawa, A.
Nishida, J. Am. Chem. Soc. 2003, 125, 7484; f) I. S.
Young, A. M. Kerr, J. Am. Chem. Soc. 2007, 129, 1465;
g) J. T. Greshock, W. A. Grubbs, M. R. Williams, Tetra-
hedron 2007, 63, 6124; h) L. Zhou, Z. Li, Y. Zou, Q.
Wang, I. A. Sanhueza, F. Schoenebeck, A. Goeke, J.
Am. Chem. Soc. 2012, 134, 20009; i) D. G. Brown, P. R.
Bernstein, Y. Wu, R. A. Urbanek, C. W. Becker, S. R.
Throner, B. T. Dembofsky, G. B. Steelman, L. A. Lazor,
C. W. Scott, M. W. Wood, S. S. Wesolowski, D. A.
Nugiel, S. Koch, J. Yu, D. E. Pivonka, S. Li, C. Thomp-
son, A. Zacco, C. S. Elmore, P. Schroeder, J. W. Liu,
C. A. Hurley, S. Ward, H. J. Hunt, K. Williams, J.
McLaughlin, V. Hoesch, S. Sydserff, D. Maier, D. Ahar-
ony, ACS Med. Chem. Lett. 2013, 4, 46.
[4] a) R. B. Homer, C. D. Johnson, in: Chemistry of
Amides, (Ed.: J. Zabicky), Interscience, New York,
1970; b) Reductions in Organic Chemistry, (Ed.: M.
Hudlicky), John Wiley & Sons, New York, 1984; c) J.
Seyden-Penne, Reductions by Alumino and Borohy-
drides in Organic Synthesis, 2nd edn., Wiley, New
York, 1997; d) H. C. Brown, W. R. Heydkamp, E.
Breuer, W. S. Murphy, J. Am. Chem. Soc. 1964, 86,
3566; e) H. C. Brown, P. Heim, J. Org. Chem. 1973, 38,
912; f) Y. Tsuda, T. Sano, H. Watanabe, Synthesis 1977,
652; g) S. Kano, Y. Tanaka, E. Sugino, S. Hibino, Syn-
thesis 1980, 695; h) S. R. Warm, P. T. Thorsen, M. M.
Kreevey, J. Org. Chem. 1981, 46, 2579; i) H. C. Brown,
Y.-M. Choi, S. Narasimhan, J. Org. Chem. 1982, 47,
3153; j) W. Stephen, B. Ganem, J. Am. Chem. Soc.
1982, 104, 6801; k) G. W. Gribble, C. F. Nataitis, Org.
Prep. Proc. Int. 1985, 17, 317; l) J. O. Osby, B. Ganem,
Tetrahedron Lett. 1985, 26, 6413; m) S. Itsuno, Y. Sakur-
ai, K. Ito, Synthesis 1988, 995; n) S. Itsuno, Y. Sakurai,
K. Shimizu, K. Ito, J. Chem. Soc. Perkin Trans. 1 1989,
1548; o) M. B. Hercouet, M. Le Corre, Synth. Commun.
1991, 21, 1579; p) S. Narasimhan, S. Madhavan, K. G.
Prasad, J. Org. Chem. 1995, 60, 5314; q) W. G. Gribble,
Chem. Soc. Rev. 1998, 27, 395; r) H. Akamatsu, S. Ku-
sumoto, K. Fukase, Tetrahedron Lett. 2002, 43, 8867;
s) S.-H. Xiang, J. Xu, H.-Q. Yuan, P.-Q. Huang, Synlett
2010, 1829.
[6] a) G. Barbe, A. B. Charette, J. Am. Chem. Soc. 2008,
130, 18; b) G. Pelletier, W. S. Bechara, A. B. Charette,
J. Am. Chem. Soc. 2010, 132, 12817.
[7] a) J. E. McMurry, Chem. Rev. 1989, 89, 1513; b) D.
Lenoir, Synthesis 1989, 883; c) A. Fürstner, B. Bogda-
novic, Angew. Chem. 1996, 108, 2582; Angew. Chem.
Int. Ed. Engl. 1996, 35, 2442; d) F. T. Ladipo, Curr. Org.
Chem. 2006, 10, 965; e) J. McMurry, M. Silvestri, M.
Fleming, T. Hoz, M. Grayston, J. Org. Chem. 1978, 43,
3249.
[8] A. Fürstner, A. Hupperts, A. Rock, E. Janssen, J. Org.
Chem. 1994, 59, 5215.
[9] J. Li, J. Chen, H.-B. Chen, W.-X. Chen, Synth.
Commun. 1998, 28, 1281.
[10] R. Dams, M. Malinowski, I. Westdorp, H. Y. Geise, J.
Org. Chem. 1982, 47, 248.
[11] M. Malinowski, L. Kaczrnareka, F. Rozploch, J. Chem.
Soc. Perkin Trans. 2 1991, 879.
´
[12] L. E. Aleandri, B. Bogdanovic, A. Gaidies, D. J. Jones,
[5] For recent examples of reductions of amides in organic
synthesis, see: a) D. T. Cushing, F. J. Sanz-Cervera,
M. R. Williams, J. Am. Chem. Soc. 1993, 115, 9323;
b) H. Sugimoto, Y. Iimura, Y. Yamanishi, K. Yamatsu,
J. Med. Chem. 1995, 38, 4821; c) B. M. Trost, R. C.
S. Liao, A. Michalowicz, J. Rozi›re, A. Schott, J. Orga-
nomet. Chem. 1993, 459, 87.
[13] C. Villiers, A. Vandais, M. Ephritikhine, J. Organomet.
Chem. 2001, 617–618, 744.
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A Convenient and General Reduction of Amides to Amines
with Low-Valent Titanium
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Adv. Synth. Catal. 2013, 355, 1 – 7
Tongxin Zhang, Yan Zhang, Weixi Zhang, Meiming Luo*
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