Direct Synthesis of 2-Formylpyrrolidines, 2-Pyrrolidinones and 2-Dihydrofuranones via Aerobic Copper-Catalyzed Aminooxygenation and Dioxygenation of 4-Pentenylsulfonamides and 4-Pentenylalcohols

Article abstract of DOI:10.1021/jacs.7b05680

A new method for the direct conversion of 4-pentenylsulfonamides to 2-formylpyrrolidines and a 2-ketopyrrolidine has been developed. This transformation occurs via aerobic copper-catalyzed alkene aminooxygenation where molecular oxygen serves as both oxidant and oxygen source. The 2-formylpyrrolidines can further undergo oxidative carbon-carbon bond cleavage in situ upon addition of DABCO, providing 2-pyrrolidinones. These transformations have been demonstrated for a range of 4-pentenylsulfonamides. 4-Pentenylalcohols also undergo oxidative cyclization to form γ-lactones predominantly. The reaction is chemoselective, oxidizing one alkene in the presence of others, and is compatible with several functional groups. Application of these reactions to the formal syntheses of baclofen and (+)-monomorine was demonstrated.

Full text of DOI:10.1021/jacs.7b05680

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Communication
Direct Synthesis of 2-Formylpyrrolidines, 2-Pyrrolidinones and 2-
Dihydrofuranones Via Aerobic Copper-Catalyzed Aminooxygenation
and Dioxygenation of 4-Pentenylsulfonamides and 4-Pentenylalcohols
Tomasz Wdowik, and Sherry R Chemler
J. Am. Chem. Soc., Just Accepted Manuscript • DOI: 10.1021/jacs.7b05680 • Publication Date (Web): 05 Jul 2017
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Journal of the American Chemical Society
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Direct Synthesis of 2-Formylpyrrolidines, 2-Pyrrolidinones and 2-
Dihydrofuranones Via Aerobic Copper-Catalyzed Aminooxygena-
tion and Dioxygenation of 4-Pentenylsulfonamides and 4-
Pentenylalcohols
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Tomasz Wdowik and Sherry R. Chemler*
Department of Chemistry, State University of New York at Buffalo, Buffalo, NY 14260, United States
Supporting Information Placeholder
Scheme 1. Aminooxygenation of Alkenes/Oxidative
C-C Bond Cleavage
ABSTRACT: A new method for the direct conversion
of 4-pentenylsulfonamides to 2-formylpyrrolidines and a
2-ketopyrrolidine has been developed. This transfor-
mation occurs via aerobic copper-catalyzed alkene ami-
nooxygenation where molecular oxygen serves as both
oxidant and oxygen source. The 2-formylpyrrolidines
can further undergo oxidative carbon-carbon bond
cleavage in situ upon addition of DABCO, providing 2-
pyrrolidinones. These transformations have been
demonstrated for a range of 4-pentenylsulfonamides. 4-
Pentenylalcohols also undergo oxidative cyclization to
form γ-lactones predominantly. The reaction is
chemoselective, oxidizing one alkene in the presence of
others, and is compatible with several functional groups.
Application of these reactions to the formal syntheses of
baclofen and (+)-monomorine was demonstrated.
O2, [Cu]
[Ru], [Os], [Au]
[O]
mCPBA
TEMPO
Ref. 3a
N
O
Ref. 8-10
Ref. 3a
NR'
R
O
O
O2, [Cu]
NHR'
(or OH)
NR'
this work
NR'
(or O)
R
R
R
e.g., mCPBA
OH
[O]
or [Pd], H2O2
O2, [Cu]
NR'
R
this work
Ref. 4
Another strategy for the synthesis of N-heterocyclic al-
dehydes from alkenes includes aminohydroxyla-
tion/cyclization and subsequent oxidation of the result-
ing alcohol.4 Related studies report aerobic Au- and Fe-
catalyzed synthesis of oxazole aldehydes,5 or aerobic
Cu-catalyzed dehydrogenative aminooxygenation af-
fording non-enolizable N-heterocyclic aldehydes.6 Elec-
trochemical-chemical oxidation has also been used, pro-
ducing 2-phenyl pyrrolidinyl and piperidinyl ketones
from the corresponding phenyl-substituted unsaturated
sulfonamides in the presence of DMSO.7
Aerobic copper facilitated organic reactions provide
practical solutions for the syntheses of a broad range of
organic molecules and have been the subject of intensive
research.1 The range of copper oxidation states enables
access to transformations that required both single and
two-electron activation mechanisms. Molecular oxygen
used in these reactions is often considered an ideal oxi-
dant due to its low environmental impact and high atom
economy. Significant natural abundance of copper and
oxygen also make them better choices in comparison
with more precious metal or organic oxidant combina-
tions, especially when large-scale processes are in-
volved. Unactivated alkenes are useful substrates that
can be transformed via copper-catalyzed difunctionaliza-
tion into a variety of N- and O-heterocycles.2 In one of
these approaches we developed an aerobic aminooxy-
Herein, we disclose a direct transformation of 4-
pentenyl sulfonamides into 2-formylpyrrolidines via
aerobic copper catalyzed aminooxygenation. A slight
modification of the reaction conditions leads to the syn-
thesis of the corresponding γ-lactams or γ-lactones that
previously were available from identical starting materi-
als but required use of more expensive ruthenium,8 os-
mium,9 or gold catalysts.10
While Cu-catalyzed alkene aminooxygenation reac-
tions dependent on stoichiometric terminal oxidants like
PhI(OAc)2 or TEMPO have strong literature precedent,11
few aerobic Cu-catalyzed aminoxygenations that use
molecular oxygen as both reactant and terminal oxidant
ganation
reaction
leading
to
(2,2,6,6-
tetramethylpiperidin-1-yl)oxyl (TEMPO) adducts that
can be subsequently converted to aldehydes (Scheme
1).3
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Page 2 of 5
have been reported,12 and none provide the aldehydes cently been demonstrated.14 Using CuCl alone allowed
1
2
3
4
5
6
7
8
and lactams observed in this study (vide infra).
formation of aldehyde 2a as a major product (Table 1,
entries 8 and 9). When CuCl or CuCN is combined with
bis(oxazoline) ligand L, the major product is lactam 3a
(Table 1, entries 5 and 6). Surprisingly, use of other bi-
dentate ligands lowers both reactivity and selectivity
(Table 1, entries 10 and 11). High selectivity towards
lactam 3a can also be achieved by addition of a catalytic
amount of 1,4-diazabicyclo[2.2.2]octane (DABCO).
This can be done after the first step of the reaction, when
formation of aldehyde 2a is complete (disappearance of
1a monitored by TLC, Table 1, entry 7). In this case, for
most substrates, use of ligand is not necessary (Table 2,
conditions A). Use of DABCO likely accelerates depro-
tonation of the aldehyde, which was shown to be the
rate-determining step in a related study on Cu-catalyzed
C-C oxidative cleavage of aldehydes to ketones.15
4-Pentenylsulfonamide 1a was thus subjected to vari-
ous Cu(I) and Cu(II) catalysts, ligands, additives and
bases in PhCH3 or PhCF3 under oxygen atmosphere (1
atm, balloon) at 105-120 °C as illustrated in Table 1 (see
Supporting Information for full optimization screen).
Table 1. Optimization of the Reaction Conditions
9
O
NTs
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
O
[Cu] (20 mol%)
O2
+
+
NTs
(1 atm)
NHTs
O
ligand, 4 Å MS
5-43 h
1a
2a
3a
O
N
L =
N
Producta
1a 2a
Cu salt
(20
mol%)
Entry
Ligand/base
3a
We employed the optimal lactam synthesis conditions
(Table 1, entries 5, 7, and ligand free conditions A in
Table 2) in the syntheses of several γ-lactams (Table 2).
1b
2b
3b
4b
Cu(OTf)2 Bis(oxazoline) (L) 57 25
18
59
39
47
CuI
L
L
L
41
0
Table 2. Reaction Scope for Synthesis of 2-Pyrrolidinones
CuBr
CuCN
45 16
47
6
6
6
O
[Cu]
O2
(1 atm)
+
(conditions A, B, C, or D)
88
(62)
NR'
NHR'
5c
CuCN
L
R
R
10-43 h
1
3
6b
7d
CuCl
CuCl
L
0
20
0
80
O
O
O
O
NTs
NTs
NTs
NTs
L + DABCO
91
(66)
9
Ph
3d, 63%a
3b, 60%a
3c, 59%a
3e, 59%a
8b
9c
CuCl
CuCl
CuCl
–
–
0
0
77
91
23
9
Bn
O
O
O
Cl
NR’
NTs
3j, 46%a
NTs
1,10-
phenanthroline
10e
65 10
25
R'
3f, 57%a
3a, Ts, 66%b
3g, Ns, 48%c
3h, Ms, 52%c
11e
CuCl
2,2’-bipyridine
39 22
39
3i, 3,5-di-t-Bu-4-OMe-C6H2SO2, 54%d
1
aRelative ratio based on crude H NMR analysis; (isolated
percent yield). bReaction run in PhCH3 at 105 °C for ca. 20
h. Reaction run in PhCH3 at 120 °C for 41 h (entry 5) and
5 h (entry 9). Reaction run in PhCF3 at 120 °C for 8 h, 15
mol% of CuCl, 17 mol% of L and 40 mol% of DABCO
(added after 5 h) were used. Reaction run in PhCF3 at 105
°C for 22 h. Ligands were complexed with [Cu] for 2 h at
60 °C prior to addition of reagents.
aConditions A: 1. CuCl (20 mol%), PhCH3, 105 °C, 4 Å
MS (reaction times 5-16 h, see Supporting Information for
each reaction); 2. + DABCO (40 mol%) for 3-10 h. bCondi-
tions B: 1. CuCl (15 mol%), L (17 mol%), PhCF3, 120 °C,
c
d
e
c
4 Å MS for 5 h; 2. + DABCO (40 mol%) for 3 h. Condi-
tions C: CuCN (20 mol%), L (22 mol%), PhCH3, 120 °C, 4
Å MS for 41 h. Conditions D: 1. CuCl (20 mol%), L (22
d
Under these conditions, varying amounts of aldehyde 2a
and lactam 3a were formed. From this screen, we con-
cluded that the copper source, ligand choice, and pres-
ence or absence of base have the most important impact
on reactivity and selectivity. Only CuCl and CuCN ena-
bled full conversion (Table 1, entries 5-9) but use of
CuCN required longer reaction time (~40 h vs. ~20 h)
and higher temperature (120 °C vs. 105 °C) compared to
CuCl. The higher reactivity of CuCl might be explained
by it relatively lower activation energy in end-on O2
coordination via a di-µ-chloro complex.13 Application of
CuCl as a catalyst for aerobic oxidative C-C bond cleav-
age in the synthesis of lactones from hemiketals has re-
mol%), PhCF3, 105 °C, 4 Å MS for 17 h; 2. + DABCO (34
mol%) for 3 h. Ligands were complexed with [Cu] for 2 h.
The reaction is compatible with both aliphatic and aro-
matic substituents at positions 1, 2, and 3 of the 4-
pentenylsulfonamides and affords the products with
moderate to good yields. The reaction works for 4-
chlorophenylpentenyl sulfonamide 1f, which is an in-
termediate in the synthesis of baclofen, a skeletal muscle
relaxant (Scheme 2).8b Additionally, the reaction is
compatible with another alkene present in the molecule
leading to chemoselective formation of lactams 3c and
3e. This chemoselectivity would be challenging to ac-
cess via the alternative Ru-based approach. N-tosyl-2-
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Journal of the American Chemical Society
allylaniline did not provide much of the corresponding
lactone under cyclization/oxidation conditions A, Table
2 (complex mixture obtained, not shown).
tion position of the 4-pentenylsulfonamide. A single
diastereomer (cis) was observed in the crude H NMR
spectra of 2,5-pyrrolidines (dr >20:1) (Table 4).
1
1
2
3
4
5
6
7
8
Scheme 2. Formal Syntheses of Baclofen and (+)-
Monomorine
O2
CuCl (20 mol%)
O
O
L (22 mol%)
O
NTs
NHTs
PhCH3, 105 °C
4 Å MS
NTs
O
Ref. 8b
Cl
OH
NH2
Cl
2a
3a
1a
NTs
(2 steps)
9
baclofen
3f
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
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34
35
36
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41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
H
Ref. 17
O
N
NTs
(4 steps)
(+)-monomorine
2q
Using similar conditions the method can be extended
to the synthesis of γ-lactones from unsaturated alcohols
(Table 3). When allylbenzene derivative 4b’ was used,
the γ-lactone 5b was obtained, which suggests isomeri-
zation of the double bond under these conditions.
Figure 1. Kinetic Profile of Aminooxygenation/Oxidative
C-C Bond Cleavage
Table 3. Reaction Scope for Synthesis of 2-
Dihydrofuranones
Table 4. Reaction Scope for Synthesis of 2-
Formylpyrrolidines and 2-Ketopyrrolidine
O
R''
[Cu]
[Cu]
O2
+
R''
(conditions A, B, or C)
4-24 h
O
(conditions A or B)
28-42 h
OH
O
O2
(1 atm)
+
R
R
(1 atm)
NR'
NHR'
4
5
R
R
1
2
O
O
O
O
O
R
R
O
O
Ph
O
Ph
NTs
O
NTs
Ph
5a, 51%a
5c, 43%b
70%b
OH
43%b
5b
NTs
(±)
(±)
O
R
R
2b, Me, 68%a (dr > 20:1)
2k, i-Pr, 70%a (dr > 20:1)
2l, t-Bu, 59%a (dr > 20:1)
2m, Bn, 60%a (dr > 20:1)
2n, CH2CH2SCH3, 40%a (dr > 20:1)
2o, CH2OBn, 72%a (dr > 20:1)
2p, CH2OTBDMS, 53%a (dr > 20:1)
2r, 39%a (dr > 20:1)
2t, Ph, 46%a (dr 6:1)
2j, Bn, 61%a (dr 4.8:1)
OH
4b
4b’
aConditions A: CuCN (20 mol%), L (22 mol%), PhCH3,
120 °C, 4 Å MS. Conditions B: CuCl (15 mol%), L (17
mol%), PhCF3, 120 °C, 4 Å MS. See Supporting Infor-
mation for individual reaction times.
O
b
O
NTs
N
Ts
O
NTs
2e, 53%a (dr 1.5:1)
2u, 35%a
2q, 61%a (dr > 20:1)
1 g scale reaction
Ph
We next investigated the possibility that aldehyde 2a
was an intermediates in the formation of lactam 3a.
Submitting 2a to the reaction condition resulted in for-
mation of 3a (see Scheme 4, vide infra, for a related ex-
periment). This observation was consistent with a reac-
tion kinetic profile that shows initial increase of alde-
hyde concentration that is later consumed in the lactam
formation (Figure 1).
O
O
O
R
NTs
NTs
NTs
R
(±)
2c, 67%a (dr > 20:1)
2v, 49%c
2s, Ph, 64%a (dr 2.0:1)
2f, 4-Cl-C6H4, 62%a (dr 1.9:1)
O
O
NR’
NTs
R’
Ph
(±)
2a, Ts, 62%b
Performing the reaction without ligand or base present
is sufficient to prevent excessive lactam formation and
to obtain the aldehyde in moderate to good yields (Table
1, entries 8 and 9). Ligand free conditions were tested
for a variety of alkenes and proved their applicability to
substrates containing another double bond (2c and 2e),
chloride (2f), thioether (2n), ether (2o, 2p, and 2i), nitro
group (2g) and furan (2r). The selectivity and stereo-
chemistry of the major product depend on the substitu-
2g, Ns, 42%b
2d, 82%a (dr > 20:1)
2i, 3,5-di-t-Bu-4-OMe-C6H2SO2, 54%b
aConditions A: CuCl (20 mol%), PhCH3, 105 °C, 4 Å MS.
bConditions B: CuCl (20 mol%), PhCH3, 120 °C, 4 Å MS.
cConditions C: CuCl (15 mol%), L (17 mol%), PhCF3, 120
°C, 4 Å MS. See Supporting Information for individual
reaction times.
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Poor diastereoselectivity (up to dr = 2:1) was found for Aldehyde 2a can either be isolated or, in the presence
1
3,5-pyrrolidines 2s and 2f. Moderate diastereoselectivity
(dr ~5:1) favoring trans products 2t and 2j was observed
for 3,5-pyrrolidines. These stereochemical patterns are
similar to those previously reported by us for Cu-
catalyzed alkene aminoxygenation/cyclization using a
TEMPO/O2 oxidative system.16 Use of the (R)-(+)-2,2’-
isopropylidenebis(4-phenyl-2-oxazoline) ligand gave 2a
in a promising 25% yield and 44% ee (not shown, see
Supporting Information for details). N-tosyl-2-
allylaniline provided aldehyde 2u in a modest 35%
yield. Transformation of an internal alkene into ketone
2v was possible with addition of ligand L, however full
conversion was not achieved. In all of these reactions the
remainder of mass can be accounted for by some for-
mation of lactam 3 (as in Table 2), some formation of
the corresponding amino alcohol and amino chloride,
and in some instances remaining starting material (see
Supporting Information for details).
of in situ formed hydroxide or external base (DABCO)
is transformed into copper(II) enolate VI. Reaction of
the enolate with molecular oxygen gives peroxy inter-
mediate VIII and then IX.18 Oxidative C-C bond cleav-
age then occurs to form lactam 3a and carbon monoxide.
The CO was detected by mass spectrometry. In addition
we performed labeling studies with oxygen-18 to detect
the source of oxygen in the final products (Scheme 4). In
agreement with the proposed mechanism, we observed
labeled lactam 3a’ and labeled carbon monoxide. These
studies do not support formation of carbon monoxide
from C-C bond cleavage of the 2-formylpyrrolidine car-
bonyl via an acyl radical15 but rather are consistent with
a mechanism involving cyclic peroxo intermediates VIII
and IX.18
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
Scheme 4. Mechanistic Investigation
18O2
18O
NTs
CuCl (40 mol%)
DABCO (78 mol%)
PhCH3, 120 °C
4 Å MS, 3 h
O
This aminooxygenation was performed on gram scale
(3.4 mmol) providing aldehyde 2q in 61% yield. Alde-
hyde 2q is an intermediate in the synthesis of (+)-
monomorine (Scheme 2).17 This modification reduced
our previous formal synthesis of that trail pheromone by
one step.16a
C18
O
+
NTs
2a
M = 281
3a’
M = 269
M = 30
found:
30 [M]+
found:
304 [M + Na]+
found:
270 [M + H]+
In conclusion, we developed the first direct method of
transforming 4-pentenylsulfonamides into 2-
We hypothesize that the reaction starts with oxidation
of copper(I) to copper(II) by O2. Copper(II)-catalyzed
alkene cis-aminocupration then affords an unstable or-
ganocopper(II) intermediate II that undergoes C-Cu ho-
molysis to give primary radical III (Scheme 3).3 The
radical reacts with molecular oxygen and leads to for-
mation of aldehyde 2a.
formylpyrrolidines, a reaction that can occur in high
diastereoselectivity and provide useful heterocyclic in-
termediates. A slight change of reaction conditions al-
lows the aldehyde to undergo further reaction with mo-
lecular oxygen leading to C-C oxidative bond cleavage
to access the corresponding lactams and lactones. This
work extends the scope of aerobic oxidative organic
transformations and provides insight into further poten-
tial reaction developments.
Scheme 3. Proposed Mechanism of Aminooxygena-
tion/Oxidative C-C Bond Cleavage
CO
ASSOCIATED CONTENT
H
C
+
O
Supporting Information
The Supporting Information is available free of charge on
the ACS Publications website at DOI:
[Cu(II)]OH
O[Cu(II)]
O
N
Ts
3a
[Cu(II)]
NTs
AUTHOR INFORMATION
Corresponding Author
II
[Cu(II)]
H
O
[Cu(II)]
TsN
O
NHTs
1a
O
N
Ts
*E-mail: schemler@buffalo.edu.
Notes
The authors declare no competing financial interest.
N
Ts
O
O
[Cu(II)]
O2
[Cu(I)]
LIGAND
CuCl
III
I
IX
[Cu(II)]
O2
N
Ts
O
VIII
O2
O
O
ACKNOWLEDGMENT
N
Ts
[Cu(I)]
O
IV
We thank the National Institute of General Medical Sci-
ence for support of this work (GM 078383) and the Bu-
reau of Educational and Cultural Affairs of the U.S. De-
partment of States for a Fullbright fellowship to T.W. We
thank Drs. Alice Bergmann and Valerie Frerichs (UB in-
strument center) for help with the mass spectrometry exper-
iments.
N
Ts
VII
O
OH
or DABCO
OH
[Cu(II)]
N
Ts
V
O[Cu(II)]
N
Ts
O
[Cu(I)]
-H2O
VI
N
Ts
2a
REFERENCES
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