Copper-Catalyzed Regio- and Stereoselective Ring-Opening of Cyclic Sulfamidates with Grignard Reagents assisted by Lithium Chloride

Article abstract of DOI:10.1002/adsc.201400850

Copper-catalyzed ring-opening reactions of cyclic 1,2-sulfamidates with a wide range of Grignard reagents have been investigated. The use of lithium chloride as an additive is essential to activate CO bond cleavage. The reaction represents highly regio- and stereoselective, and thus allows for efficient synthesis of enantioenriched α-branched benzylamine derivatives. Furthermore, we demonstrated that the products are potential to be used as building blocks for the preparation of wide range of nitrogen-containing heterocycles.

Full text of DOI:10.1002/adsc.201400850

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DOI: 10.1002/adsc.201400850
Copper-Catalyzed Regio- and Stereoselective Ring-Opening of
Cyclic Sulfamidates with Grignard Reagents assisted by Lithium
Chloride
Pitchaiah Arigala,a Venkata S. Sadu,b In-Taek Hwang,a Jin-Soo Hwang,a
Chul-Ung Kim,a and Kee-In Leea,b,*
a
Green Chemistry Division, Korea Research Institute of Chemical Technology, Taejon 305-600, Korea
E-mail: kilee@krict.re.kr
b
Department of Green Chemistry and Environmental Biotechnology, University of Science and Technology, Taejon
305-333, Korea
Received: July 28, 2014; Revised: February 5, 2015; Published online: May 13, 2015
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201400850.
Abstract: Copper-catalyzed ring-opening reactions
of cyclic 1,2-sulfamidates with a wide range of
Grignard reagents have been investigated. The use
of lithium chloride as an additive is essential to acti-
tion of amines,[3e] access to a diverse range of a-
branched benzylamines for the construction of com-
plex molecules is rather limited. In this regard, ring-
opening of aziridines or its synthetic equivalents,
cyclic sulfamidates are the most attractive.[4] However,
transition metal-catalyzed cross-coupling of 2-arylazir-
idines preferentially occurs at the more substituted
position of the aziridine to furnish b,b-disubstituted
amines.[5] In addition, activated 2-arylaziridine is ring-
opened at the benzylic postion by the nucleophilic att-
tack with organometallic reagents[6] or heteroatom
nucleophiles through Lewis acid activation.[7]
À
vate C O bond cleavage. The reaction represents
highly regio- and stereoselective, and thus allows
for efficient synthesis of enantioenriched a-
branched benzylamine derivatives. Furthermore, we
demonstrated that the products are potential to be
used as building blocks for the preparation of wide
range of nitrogen-containing heterocycles.
Keywords: CuI/LiCl; inversion; ring-opening; sulfa-
midate; a-branched benzylamine
Recently, transition metal catalyzed cross coupling
reaction with electrophile bearing an oxygen-based
leaving group has emerged to be one of the most
À
powerful methods for construction of C C bonds.
Oxygen leaving groups are widely employed in cross-
coupling reactions of aryl carbamates, carbonates, and
2
bond cleavage).[8,9] However,
À
The chiral amines are ubiquitous molecules in chemis- sulfamates (Csp
try and biology, since are the vital entities in human there are few examples especially for the alkyl elec-
O
3
À
living organism by controlling and maintaining a com- trophiles bearing such oxygen leaving groups (Csp
O
plex set of biological processes. As a consequence, bond cleavage),[10] even transition metal catalysts can
much attention has been devoted for the stereoselec- now promote the coupling of primary and secondary
tive generation of nitrogen-containing chiral centers, alkyl halides or pseudohalides.[11]
whereby the addition of organometallic reagents to
Alternatively, ring-opening of cyclic sulfamidates
C=N double bonds is of great synthetic interest.[1] In with heteroatom nucleophiles has been long sought
particular, a-branched benzylamines are frequently for the construction of N-heterocycles.[12] In addition,
found as structural motifs in natural products (e. g., the ring-opening of the sulfamidates with stabilized
isoquinoline alkaoids) and biologically active mole- carbanions proceeds selectively at the O-bearing
cules across many therapeutic areas.[2] While numer- carbon centre by a SN2 pathway.[13] Even with the ob-
ous methods for the synthesis of this motif have been vious synthetic utility, introduction of non-activated
reported, ranging from transition metal-catalyzed carbon nucleophiles into sulfamidates has been less
asymmetric hydrogenation of enamides and enamine- widely exploited, comparing to its congeneric sulfami-
s[3a] to Pd-catalyzed arylation of 9-aminofluorene-de- dites.[14] The major challenge in ring-opening of sulfa-
rived imines[3b] and a-(acetylamino)benzylboronic es- midates with Grignard reagent was regioselectivity, in
ters,[3c] and more recent photoredox-catalyzed decar- which a bond cleavage took place at among C O,
À
boxylative arylation of a-amino acids[3d] and a-aryla- S O, and S N bonds depending on the conditions
À
À
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Pitchaiah Arigala et al.
Table 1. Catalysts screening and additives effect.[a]
Entry
Catalyst/Additive
Yield[b]
2a
2a1
2a2
Scheme 1. Ring-opening of a sulfamidate with Grignard re-
agent.
1
2
3
4
5
6
7
8
none[c]
Li2CuCl4
Ni(acac)2
Ni(cod)2
NiCl2(PPh3)2
NiCl2(dppe)
NiCl2(dppp)
NiCl2(dppb)
CuBr-SMe2
CuI
CuTC
Cu(OTf)2
NiCl2(dppp)/
LiCl (5 mol%)
CuI (10 mol%)/
LiCl (5 mol%)
–
–
–
nd
nd
nd
13
38
73
32
34
64
43
nd
21
54
54
62
37
37
16
45
32
14
12
41
36
45
nd
nd
nd
nd
nd
nd
16
17
28
40
47
employed (Scheme 1).[15] In order to address the prob-
lems associated with the ring fission of 4-arylsulfami-
date, we thoroughly investigated the distribution of
three possible products upon changes associated with
the N-blocking groups, catalysts, and additives.
Herein, we disclose a copper-catalyzed regio- and ste-
reoselective ring-opening of cyclic 1,2-sulfamidates
with Grignard reagents assisted by lithium chloride.
Initial investigation revealed that a sulfamidate
could be activated by a relatively electron-rich group
on the nitrogen, thus allowing for the nucleophilic
9
10
11
12
13
14
89
nd
7
[a]
À
attack on the carbon atom to provide the C O cleav-
Unless otherwise indicated, the reaction was carried out
on a 0.25 mmol scale of 1a using 5 mol% of catalyst and
was quenched with 2N citric acid solution.
Yield of isolated product.
age product, after acidic hydrolysis (see Supporting
Information). In the absence of a metal catalyst, no
product formation was observed (Table 1, entry 1).
The soluble copper reagent Li2CuCl4 is known to
couple halides or sulfonates with Grignard reagents,[16]
[b]
[c]
No reaction was observed, nd=not detected.
however, surprisingly the reaction of 1a resulted in plied to the reaction, LiCl proved to be particularly
hydrolysis of the sulfonyl group (i.e., 2a1) along with efficient in this transformation, when CuI was em-
the formation of aziridine (2a2). It is obvious that ployed (see Supporting Information). To our delight,
without a catalyst the Grignard reagent preferentially the reaction of 1a afforded 2a in 89% yield in the
attacks the sulfur atom (entry 2). Nickel(0) complexes presence of CuI (10 mol%) and LiCl (5 mol%)
such as Ni(acac)2, Ni(cod)2 only gave 2a1. In the pres- (entry 14).
ence of NiCl2(dppp), nucleophilic attack predomi-
Under the optimized conditions, we next examined
nantly takes place at the carbon atom; thus the reac- the efficacy and scope of the reaction with respect to
tion gave the coupled product 2a in 73% yield along both aryl sulfamidates and Grignard components with
with 2a1 in 16% yield (entry 7). Nickel(II) catalysts steric demands (Table 2). The corresponding products
containing bidentate diphosphines exhibited much (2b–2h) were obtained in excellent to good yields
higher activity than the monodentate NiCl2(PPh3)2; from primary, secondary, and tertiary alkyl Grignard
moreover, the catalytic activity of NiII complexes de- reagents, for which there were no rearranged prod-
pends largely on the size of the chelate ring. Various ucts. It is worth noting that the coupling of alkyl elec-
copper salts were also tested for this transformation; trophiles with secondary and tertiary nucleophiles is
among them, CuI was more effective than all other still challenging because of the difficulty in achieving
CuI catalysts under the same reaction conditions transmetalation from sterically encumbered nucleo-
(entry 10).[17] However, CuII catalysts could not gener- philes, and the propensity to isomerisation of metal
ate the desired product. Thus, the catalytic activity alkyl species by b-H elimination.[11] The coupling with
strongly depends upon the nature of the ligands and functionalized Grignard reagents also worked well
oxidation states of metal complexes. Among the dif- (2i–2l). Not only aryl and alkyl, but also allyl
ferent catalysts applied to the reaction, NiCl2(dppp) Grignards could be coupled (2m–2o) with an excel-
and CuI proved to be moderately effective in this lent yield. Interestingly, vinyl Grignard reaction also
transformation, however, two or three major addition underwent ring-opening to give 2p, previously diffi-
products were commonly observed. To overcome this cult to obtain. Benzyl and ethynyl Grignard reagents
challenge, we therefore focused our attention on the failed, but the reason is unclear. The substrates con-
effect of salt additives commonly used in the cross- taining heteroaryl such as furyl and thienyl groups
coupling reactions. Among the different additives ap- were also participated in high yield. Most a-branched
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Copper-Catalyzed Regio- and Stereoselective Ring-Opening
Table 2. Regioselective ring-opening of cyclic 1,2-sulfami-
dates with Grignard reagents.
Table 3. Stereoselective ring-opening of 4,5-disubstituted sul-
famidates with Grignard reagents.
Entry Sulfamidate[a] Product
Yield[b] ee[c]
[d]
1
87
82
–
2
3
75
89
85
98
98
98
98
4
5
6
97
99
[a]
A reducing product 2hꢀ (R=H) was found in 39% yield.
[b]
Aziridine 2a2 was also isolated in 21% yield.
[c]
The corresponding aziridine and byproducts were formed
7
8
89
90
99
99
but not isolated.
benzylamine products were the sole products, while
aziridines were occasionally observed, such as in case
of vinyl Grignard (2p) or when an electron-rich sub-
strate was employed (2s).
Notably, the electronic nature of N-blocking groups
of sulfamidites and sulfamidates can exert a powerful
stereodirecting effect. The N-benzyl group of the sul-
9
91
97
99
À
famidates allows for the facile cleavage of C O bond
under the Ni- or Cu-catalysis, whereas sulfinamides
10
84
87
À
could be activated for S N bond scission by an elec-
tron-withdrawing substituent on the nitrogen.[14]
We then turned our attention to the stereochemical
outcomes from the coupling with secondary sulfami-
dates. To our delight, copper-catalyzed ring-opening
of 4,5-disubstituted sulfamidates 3 with Grignard re-
[d]
11
–
[a]
Sulfamidates were prepared from the corresponding
amino alcohols measured to be as high as 99% ee, except
75% ee of 3a (see Supporting Information).
Yield of isolated product.
agents produced
4 in good to excellent yield
(Table 3). The ring-opening of (4R,5R)-3c gave
a better yield than that of (4R,5S)-3b, this is presuma-
bly due to a steric factor coming from the pre-existing
C4-substituent (entries 5 and 3). The NOE experi-
ments of 4 f revealed that the reaction occurs with in-
version of configuration. We also have double agree-
[b]
[c]
[d]
Determined by chiral HPLC analysis.
Not completely separated.
ment on the inversion of configuration without loss of their antipodes (Table 3, entries 6–11). This finding
enantiomeric purity, as judged by chiral HPLC using confirms that the present reaction for secondary sulfa-
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Pitchaiah Arigala et al.
Scheme 2. A suggested mechanism for ring-opening of sul-
famidate.
Scheme 3. Further transformations of a-branched benzyla-
mine derivatives.
midate with secondary Grignard also proceeded by an
SN2 mechanism. Thus, interestingly enough, when
chiral 1-aminoindanols are converted to functional-
ized 1-aminoindane derivatives, these can serve as im- employing currently developed powerful strategies
portant structural elements for drug investigations.[18] (Scheme 3). For example, tetrahydroazepine 5 was
The importance is that the present method provides synthesized by N-allylation of 2m, followed by ring-
a practical approach for the stereocontrolled forma- closing metathesis using the second-generation
tion of C C bonds from the ring-opening of sulfami- Grubbs catalyst.[22] In addition, 1,3-dioxane-containing
À
dates.
benzylamine 4d was subjected to catalytic hydrogena-
In terms of the control experiments, we have ruled tion in the acidic conditions to give (2S,3R)-diphenyl-
out the possibility of the involvement of a chloroamine piperidine 6. Remarkably, this reductive cyclization
intermediate through the ring opening by LiCl and proceeded via multi-step, one-pot, sequential transfor-
the presence of RMgX.LiCl complex[19] that might ac- mations including the acetal hydrolysis, followed by
count for the observed reactivity (see Supporting In- reductive amination with concomitant removal of the
formation). Recent publications have shown a remark- benzyl group.[23] Recently, aminocyclization of alkenes
able effect of LiCl in the cross-coupling reactions.[20] has been important objective for the synthesis of pi-
Our results also reveal that CuI/LiCl is a competent peridines, recognized as privileged structures in drug
catalyst for the ring-opening of sulfamidates with discovery with their wide range of biological activities.
a highly regio- and stereoselective manner. In regard Thus, homoallylic amine 4e was initially treated with
to the effect of these additives, it is believed that the NIS in tBuOH, and then followed by AgOTf and
more
nucleophilic
organocopper
species TBAF to afford piperidine 7a in 47% and pyrrolidine
(R2CuÀMgX+) could be generated via transmetalation 7b in 11% yield, as separable mixture of regioisom-
from magnesium to copper. This intermediate is sup- ers.[24] The relative stereochemistry was assigned
posed to be reactive species upon reaction with sulfa- based on NOE experiments.
midate to afford the ring-opened product, as illustrat-
Attention next turned to examining cyclocarbama-
ed in Scheme 2. On the other hand, lithium ion has tion of homoallylamine. Indeed, electrophile-induced
a strong tendency to coordinate with oxygen atom. cyclocarbamation of homoallylic carbamates has been
Apparently, copper catalysis with a cooperative assis- long sought as templates for the construction of 1,3-
tance of lithium activation of the bridge oxygen might aminoalcohol functionality. The cyclocabamation of
be a plausible explanation for the regio- and stereose- N-Cbz protected 8 induced by the treatment with I2
lective ring-opening of the sulfamidates via likely afforded a diastereomeric mixture of trans- and cis-
through a six-membered transition state.[21]
oxazinan-2-ones in a 9 to 1 ratio.[25]
To highlight the present method, we demonstrate
In summary, we have developed a new copper-cata-
the utility of the ring-opened products for synthesis of lyzed procedure for ring-opening of cyclic 1,2-sulfami-
nonracemic N-containing heterocycles. Importantly, dates with Grignard reagents. During the study, we
the a-branched benzylamines and their derivatives thoroughly investigated the distribution of three pos-
could serve as potential building block for the con- sible products upon changes associated with the N-
struction pyrrolidine, piperidine, and even azulene blocking groups, catalysts, and additives. We found
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Copper-Catalyzed Regio- and Stereoselective Ring-Opening
1.91 (d, J=6.6 Hz, 1H) ppm; 13C NMR (CDCl3, 125 MHz):
d 140.2, 139.2, 128.4, 128.3, 127.9, 127.0, 126.9, 126.3, 64.8,
41.5, 38.0 ppm; HRMS (EI) m/z [M+] calcd for C15H15N,
209.1204, found 209.1202.
that copper-catalyzed ring-opening of sulfamidates is
promoted by the use of lithium chloride presumably
by cooperative assistance. The ring-opening reaction
worked well with not only alkyl and aryl Grignards,
but also secondary/tertiary alkyl and vinyl Grignard
reagents. The present method confirmed that the re-
action between secondary sulfamidates and secondary
alkyl Grignard reagents also proceeded through an
SN2 mechanism without loss of enantiomeric purity.
This reaction represents high regio- and stereoselec-
tive, and thus allows for efficient synthesis of nonrace-
mic a-branched benzylamine products. Interestingly
enough, the present method provides a practical ap-
Acknowledgements
This study was supported by the KRICT Research Program
(SI-1301) sponsored by the Ministry of Strategy and Finance,
and by the grant from the Industrial Source Technology De-
velopment Program (2014–10042591) of the Ministry of
Trade, Industry and Energy, Republic of Korea. The authors
thank the reviewers for their helpful advice and crucial com-
ments on the mechanism.
À
proach for the stereocontrolled formation of C C
bonds from the ring-opening of sulfamidates. Further-
more, we revealed that the products have the poten-
tial to be used as building blocks for the preparation
of wide range of nitrogen-containing heterocycles and
natural products.
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