Use of a benzyl ether as a traceless hydrogen donor in the anti-Markovnikov hydrofunctionalization of alkenes with xanthates

Article abstract of DOI:10.1039/c8cc02971g

A new protocol for the anti-Markovnikov hydrofunctionalization of alkenyl alcohol O-Bn ethers was developed using xanthates as functionalizing agents in the presence of lauroyl peroxide as a radical initiator and a stoichiometric oxidant. The benzyl group serves as a traceless hydrogen donor in the remote radical hydrogen atom transfer event during the process.

Full text of DOI:10.1039/c8cc02971g

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Use of a benzyl ether as a traceless hydrogen donor in anti-
Markovnikov hydrofunctionalization of alkenes with xanthates
Hirohito Hayashi,a Atsushi Kaga,a Bin Wang,a Fabien Gagosz*b and Shunsuke Chiba*a
Received 00th January 20xx,
Accepted 00th January 20xx
DOI: 10.1039/x0xx00000x
www.rsc.org/
A new protocol for anti-Markovnikov hydrofunctionalization of the premature reduction of the initially formed C-radical by
alkenyl alcohol O-Bn ethers was developed using xanthates as the external H-atom donor. As a consequence, most of these
functionalizing agents in the presence of lauroyl peroxide as a intermolecular processes have been conducted with
a
radical initiator and a stoichiometric oxidant. The benzyl group combination of nucleophilic C-radicals and electron-deficient
serves as a traceless hydrogen donor in the remote radical alkenes. To overcome this defect associated with the
hydrogen atom transfer event during the process.
intermolecular H-atom delivery step, we recently reported use
of a benzyl ether for the precise intramolecular hydrogen atom
transfer (HAT) via 1,5-radical shift in Cu-catalyzed
hydrotrifluoromethylation and hydroazidation of homoallylic
alcohols.6-9 During the redox catalytic process, the benzyl
group is removed as a benzaldehyde, thus serving as a
traceless protecting group of the corresponding alcohols
(Scheme 1B). Despite the general efficiency and selectivity of
the method, the employment of hypervalent iodine reagents
as C-radical precursors inherently restricted the functional
groups that could be introduced on the alkene. To circumvent
this limitation, we became interested in the use of xanthates
as a carbon radical source in combination with dilauroyl
peroxide (DLP) as a radical initiator and a stoichiometric
oxidant (Scheme 1C). The design, optimization, and substrate
scope of these processes are described herein.
Chemical processes based on anti-Markovnikov
hydrofunctionalization of alkenes offer an attractive
opportunity for the production of high value fine chemicals.
Despite the synthetic potential of this approach and the
numerous developments made in this area, there still remain
challenges to functionalize non-activated alkenes in
a
regioselective fashion.1 One of the methods to realize this goal
is to use carbon-centered radicals (Scheme 1A). From a
mechanistic point of view, such a process involves the initial
addition of a C-centered radical onto the less substituted side
of a non-activated alkene, thus generating a new C-C bond in
an anti-Markovnikov manner. A subsequent delivery of a H
atom onto the resulting highly reactive carbon radical is then
required to complete the alkene hydrofunctionalization. In this
context, the Giese reaction using alkyl halides and their
derivatives as a C-radical source, and tin hydrides (typically,
Bu3SnH) as a H atom donor represents one of the most
powerful hydrofunctionalization methods.2 Processes using
tris(trimethylsilyl)silane [(TMS)3SiH]3 and borohydrides4 as a H-
atom donor, and those involving photoredox catalysis5 have
proven promising. However, an adequate polarity match is
generally required between the C-radical and the alkene in
order to favor the formation of the radical adduct and prevent
a.Division of Chemistry and Biological Chemistry, School of Physical and
Mathematical Sciences, Nanyang Technological University, Singapore 637371,
Singapore. E-mail: shunsuke@ntu.edu.sg
b.Department of Chemistry and Biomolecular Sciences, University of Ottawa, K1N
6N5, Ottawa, Canada. E-mail: fgagosz@uottawa.ca
Electronic Supplementary Information (ESI) available: Electronic Supplementary
Information (ESI) available: Experimental details, including procedures, syntheses
and characterization of new compounds; 1H and 13C NMR spectra. See
DOI: 10.1039/x0xx00000x
Scheme 1. Hydrofunctionalization of alkenes with radicals
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The degenerative addition-transfer of xanthates to alkenes, treatment of a mixture of 1a and 2a with 2.5 equiv of DLP in
which has been extensively developed by the group of Zard,10 1,2-dichloroethane at 85 °C followed by subsequent acidic
represents an extremely powerful synthetic tool for the solvolysis of the resulting ketal intermediate XI with TsOH (20
creation of new C-C bond. This widely applicable protocol mol%) in EtOH. This protocol afforded 3aa in 83% isolated
enables installation of a variety of functional groups onto yield (Scheme 3). We then surveyed the substrate scope of
alkenes with concomitant transfer of the xanthate moiety alkenes
following radical chain mechanism (Scheme 2A). To 3, various secondary alkenyl O-benzyl ethers 1b
ultimately obtain a hydrofunctionalized product III starting transformed into the corresponding hydrocyanomethylated
from xanthate , an additional step of reductive removal of the alcohols 3ba 3ga in good to moderate yields. A variety of
1
using cyanomethyl xanthate 2a. As shown in Scheme
a
-1g could be
I
-
xanthate moiety from the initially formed adduct II is required. functional groups such as a thienyl (for 3ca), a phthalimidoyl
This can be achieved using an external hydrogen atom donor (for 3da), an ethoxy carbonyl (for 3ea) as well as cleavable
such as Bu3SnH or (TMS)3SiH in combination with AIBN,11,12 ethers (for 3fa and 3ga) were tolerated. Notably, the reaction
hypophosphorous acid with AIBN,13 the triethylborane-water of alkene 1g, possessing two remote benzyl ether moieties,
system,14 or more simply isopropanol or cyclohexane in the underwent a selective 1,5-HAT (versus a potentially competing
presence of DLP.15 We surmised that the presence of a 1,6-HAT) to provide the monobenzyl ether 3ga in 57% yield.
benzyloxy group in an appropriate position of the starting Tertiary (for 3ha) and primary (for 3ia-3ja) alcohols could be
alkene IV would facilitate a subsequent HAT to the carbon- constructed in good yields. The method also allowed for 1,6-
centred radical intermediate
oxy benzyl radical VI could then be further oxidized by DLP to
oxocarbenium ion VII, that is converted into ketal VIII 16
V
(Scheme 2B). The resulting
α
-
and 1,7-HAT (for 3ka-3na) with moderate efficiency.
.
A
subsequent hydrolysis of VIII would liberate the
hydrofunctionalized product IX along with benzaldehyde and
lauric acid. Thus, anti-Markovnikov hydrofunctionalization of
alkenes (IV
→IX) could be accomplished in one-pot fashion. It
should be noted that the formation of xanthate adduct
X
would not affect the process as radical
regenerated in the presence of DLP.
V
should be
A. Degenerative addition-transfer of xanthates to alkenes
OEt
ꢀ
reductive
removal
R
H
initiator
I
+
S
S
Fn
Fn
R
S
xanthate
transfer
Fn
R
R
Fn
III
S
OEt
II
under radical chain
xanthates I
B. Working hypothesis: use of Bn ether as a H-radical donor
OEt
Ph
S
S
O
xanthate I
Fn
DLP
X
xanthate I
DLP
Ph
O
Ph
Ph
H
O
HAT
H
(> 1 equiv)
O
Fn
Fn
IV
V
VI
DLP
•
RCO2– + RCO2
“H-Fn”
Ph
Ph
O2CR
.
a The reaction were
(R = C11H23
)
H2O
Scheme 3. Scope of alkenes
1
conducted using 0.5 mmol of alkenes
with cyanomethyl xanthate 2a
and xanthate 2a (1.5 equiv) with DLP (2.5
–
RCO2
H
OH
H
H
O
O
1
Fn
Fn
Fn
equiv) in ClCH2CH2Cl (0.5 M) at 85 °C for 2-4 h, followed by solvolysis with TsOH
(20 mol%) in EtOH at 23 °C for 2 h. Unless otherwise stated, isolated yields of the
products are given based on alkenes. b The solvolysis was conducted using AcOH
–PhCHO
–RCO2H
IX
VII
VIII
c
Scheme 2. Hydrofunctionalization of alkenes with xanthates
(1.7 equiv) in H2O at 23 °C. The solvolysis was conducted using TsOH (20 mol%)
in MeOH at 23 °C.
With this working hypothesis, we initiated our studies with
the reactions of homoallylic alcohol O-benzyl ether 1a with
We next investigated compatibility of xanthates using
cyanomethyl xanthate 2a
conditions17,18
revealed
hydrocyanomethylation-debenzylation sequence is enabled by methyl (for 2c), a cyclopropyl (for 2d) or a chloromethyl (for
.
Optimization of the reaction alkene 1a or 1i under the optimal reaction conditions. The
that the desired reactions of ketonyl xanthates having a phenyl (for 2b), a
2 | J. Name., 2012, 00, 1-3
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2e) moiety led to a facile 1,5-HAT/debenzylation sequence,
providing the corresponding hydrofunctionalized alcohols
(
3ab-3ae) in good to moderate yields. The method also
allowed for the installation of an alkoxycarbonyl function as
attested by the formation of ester 3af and lactone 3ig. The
reaction with phthalimidomethyl xanthate 2h19 took place
smoothly, affording the N-protected 1,5-amino alcohol 3ah in
good yield.
a
Scheme 4 Scope of xanthates
conducted using 0.5 mmol of alkenes 1a or 1i and xanthate
2
with alkene 1a or 1i
.
The reaction were
(1.5 equiv) with
2
DLP (2.5 equiv) in ClCH2CH2Cl (0.5 M) under reflux for 2-5 h, followed by
solvolysis with TsOH (20 mol%) in EtOH at 23 °C. Unless otherwise stated,
isolated yields of the products are given based on alkenes. b 3.5 equiv of DLP was
used.
The present protocol was also found applicable to
diastereoselective HAT in the hydrofunctionalization of either
bromoalkene 1o or fluoroalkene 1p (Scheme 5A). The hydro-
ethoxycarbonylmethylation of 1o with xanthate 2f delivered
the desired product 3of in 71% yield with good 1,3-anti
diastereoselectivity (74:26). A similar behaviour was observed
a
Scheme 5. Diastereoselective HAT onto haloalkenes. The diastereomeric ratio
b
was determined by 1H NMR analysis. The diastereomeric ratio was determined
with fluoroalkene 1p
, which could be converted into
by 19F NMR analysis.
fluoroalcohol 3pa (76%, d.r. = 78:22). The observed 1,3-anti
selectivity could be attributed to the involvement of a chair-
like transition state in the HAT process with the more sterically
demanding groups preferentially adopting a pseudo-equatorial
position.20 Among the conformers leading to the HAT, that in
which the bulkier cyanoethyl or ethoxycarbonylethyl group is
located at the pseudo equatorial position would be
energetically more favourable (Scheme 5B). It is worth noting
that the resulting hydrofunctionalized product 3of could be
This work demonstrates the use of a benzyl ether as a
traceless redox active hydrogen donor in anti-Markovnikov
hydrofunctionalization of alkenes with xanthates. This
protocol, in which DLP is used both as a radical initiator and an
oxidant, allowed for the facile installation of various functional
groups onto readily available alkenyl alcohols.
This work was supported by funding from Nanyang
Technological University (for S.C.), the Singapore Ministry of
Education (Academic Research Fund Tier 1: RG2/15 for S.C.)
and the Natural Sciences and Engineering Research Council
(for F.G.). F.G. and S.C. are grateful to PHC Merlion grant
(Project 5.02.15) for the support of this collaboration project.
further transformed into
β-hydroxy N-H pyrrolidine 3of’’ by
treatment with hydrazine. This transformation involved the
initial formation of primary amine 3of’ followed by
intramolecular cyclization (Scheme 5C). Subsequent protection
of the amine moiety in 3of’’ afforded the N-Boc pyrrolidine
derivative 4of in 61% yield over two steps.21 Alternatively,
treatment of 3of’’ with NaOEt promoted its lactamization into
pyrrolizidin-3-one 5of (90%).22
Notes and references
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protection under the optimized reaction conditions resulted
in the formation of a complex mixture of unidentified
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A new protocol for anti-Markovnikov hydrofunctionalization of alkenyl alcohol O-Bn
ethers was developed using xanthates as functionalizing agents in the presence of
lauroyl peroxide as a radical initiator and a stoichiometric oxidant.