Copper-catalyzed enantioselective 1,2-borylation of 1,3-dienes

Article abstract of DOI:10.1039/c8sc01538d

A highly enantioselective Cu-catalyzed borylation of 2-substituted 1,3-dienes is reported. The use of a chiral phosphanamine ligand is essential in achieving high chemo-, regio-, diastereo- and enantioselectivity. It provides access to a variety of homoallylic boronates in consistently high yield and enantiomeric excess with 2-aryl and 2-heteroaryl 1,3-dienes as well as sterically demanding 2-alkyl 1,3-dienes. Preliminary investigations based on a non-linear effect study point to a mechanism involving more than one metal center.

Full text of DOI:10.1039/c8sc01538d

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Copper-catalyzed enantioselective 1,2-borylation of 1,3-dienes
Yangbin Liu,a Daniele Fioritoa and Clément Mazet*a
Received 00th January 20xx,
Accepted 00th January 20xx
A
highly enantioselective Cu-catalyzed borylation of 2-substituted 1,3-dienes is reported. The use of a chiral
phosphanamine ligand is essential in achieving high chemo-, regio-, diastereo- and enantioselectivity. It provides access to
a variety of homoallylic boronates in consistently high yield and enantiomeric excess with 2-aryl and 2-heteroaryl 1,3-
dienes as well as sterically demanding 2-alkyl 1,3-dienes. Preliminary investigations based on a non-linear effect study
point to a mechanism involving more than one metal center.
DOI: 10.1039/x0xx00000x
www.rsc.org/
generated upon exclusive mono-functionalization (Fig. 1, B).
Allylic boronates resulting from formal 1,4- or 4,1-
hydroborations of 2-substituted 1,3-dienes have been
Introduction
Conjugated 1,3-dienes represent
a particularly attractive
reported by the groups of Suzuki and Ritter using highly
chemo-, regio- and stereoselective Pd, Rh and Fe catalysts.7
platform for selective functionalizations. They do occur in
some natural products and have often been used as
bifunctional building blocks for the synthesis of biologically
active molecules as well as in several polymerization
processes.1,2 From a selectivity standpoint, functionalization of
1,3-dienes represents a significant challenge due to the
numerous coordination and insertion modes conceivable for a
transition metal catalyst.3 To date, efforts to develop selective
catalytic transformations have been essentially focused on
linear 1,3-dienes (i.e 4-substituted 1,3-dienes).4 Until recently,
the limited synthetic accessibility of 2-substituted 1,3-dienes
has hampered their use in the development of selective
transformations.5 Moreover, most examples were focused on
isoprene and myrcene, two readily available substrates of this
subclass of conjugated dienes. Consequently, the effect of
electronic and steric modifications has not been systematically
investigated. For instance, the introduction of an aryl instead
of an alkyl substituent at position 2- of a conjugated diene is
likely to impart substantial changes in substrate polarity
and/or in steric demand (Fig. 1, A). Our laboratory recently
reported a general procedure which streamlines access to 2-
substituted 1,3-dienes and we decided to initiate a program on
the selective functionalization of this underexplored scaffold.6
Among the approaches to functionalize 1,3-dienes,
transition metal-catalyzed hydroborations and borylations
have emerged as attractive strategies providing access to
polyfunctionalized – potentially enantioenriched – structural
motifs. For 2-substituted substrates, the selectivity challenge is
highlighted by the fact that up to 6 different isomers can be
Homoallylic boronates obtained by
a
4,3-selective
hydroboration are less common. Ito, Fout and Chirik only
described such products in studies where the focus was
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initially set on the hydroboration of cyclic 1,3-dienes and
terminal alkenes.8 To our knowledge, methods to access
products of 1,2-, 2,1- and 3,4-selective hydroboration are
absent from the current literature (Fig. 1, B). Cu/Pd-catalyzed
cooperative carboboration of alkenes represents another
emerging class of transformation which involves the transient
generation of copper-alkyl intermediates prior to
transmetalation to a palladium catalyst.9 In this context, only
few reports have placed emphasis on 1,3-dienes.10 The Brown
group recently disclosed the highly selective arylboration of
isoprene and myrcene unexpectedly leading to the exclusive
formation of A when 4-dimethylaminopyridine (DMAP) was
employed as additive (Fig. 1, D).10a Interestingly, to account for
this unusual selectivity preliminary mechanistic investigations
Table 1. Reaction optimization.a
do not support the formation of a congested Cu-σ-allyl
intermediate such as B (Fig. 1, D) but rather transmetalation to
Pd from a putative 1,4-borocupration species such as C. Within
this context, at the outset of our investigations, we aimed at
establishing
a perfectly 1,2-selective borylation of 2-
substituted 1,3-dienes to access valuable enantioenriched
homoallylic boronates.11 Herein, we describe the successful
realization of our objective with the development of a highly
chemo-, regio-, and enantioselective Cu-catalyzed borylation
of a variety of 2-substituted 1,3-dienes.
entry
1
L
solvent conv. (%)b 2a : 3a : 4ab ee 2a (%)c
L1 THF
L2 THF
L3 THF
L4 THF
L5 THF
L6 THF
L7 THF
L8 THF
L9 THF
L9 Et2O
L9 Tol.
L9 C6H5Cl
L9 C5H12
L9 C5H12
86
1 : 15 : -
1 : 3 : -
nd
2
74
5 (S)
3d
67
1 : 7 : -
21 (R)
24 (R)
4 (R)
4
81
1 : 1.5 : -
4.6 : 1.3 : 1
4 : 1 : 1
5d
63
Results and discussion
6d
80
20 (R)
43 (R)
48 (R)
67 (R)
72 (R)
70 (R)
74 (R)
70 (R)
85 (R)
90 (R)
Our study commenced by evaluating several chiral ligands for
the Cu-catalyzed borylation of 1a using prototypical reaction
conditions favoring borylcupration (B2(pin)2/MeOH; Table
7
74
6 : 1 : 2
8d
87
8 : 2 : 1
1).12,13 With ligands L1-3
, homoallylic boronate 3a was
9d
91
27 : 2.7 : 1
12 : 1 : -
13 : 1 : -
12 : 1 : -
17 : 1 : -
20 : 1 : -
20 : 1 : -
obtained predominantly along with trace amount of the
desired 1,2-borylated product 2a (conv. = 67-86%; Entry 1-3).
The commercially available bisphosphine (R)-BDPP afforded 2a
and 3a in a nearly 1:1 ratio with a low but measurable
enantioselectivity for the former (2a: 24% ee, Entry 4). Using
10d,e
11d,e
11 d,e
13 d,e
14e,g
51
83
85
either
diastereoisomers
of
the
well-established
88
phosphoramidite ligands L5 and L6
,
2a was obtained as major
77
89 (82)i
regioisomer albeit in mixture with both 3a and (E)-4a (a
product of formal 1,4-borylation) and in low ee (Entry 5-6). The
chiral heterotopic ligand (R)-Quinap L7, enabled to increase
both the relative ratio in favor of 2a as well as its enantiomeric
excess (2a: 43% ee; Entry 7). A slightly improved result was
achieved with Simplephos L8 – a structure introduced by the
Alexakis group which rapidly established itself as a ubiquitous
15f,g,h L9 C5H12
a Reaction conditions: 1a (0.12 mmol), B2(pin)2 (0.10 mmol), 0.3
b
c
M. Determined by 1H NMR using an internal standard.
Determined by HPLC using a chiral stationary phase after
oxidation to the corresponding alcohol 2’a. d 20 mol% of ligand.
e
f
g
h
0.1 M. 0.15 M. –40 °C, 40 h. CuOtBu (10 mol%), without
ligand
in
numerous
Cu-catalyzed
enantioselective
i
base. Yield over 2 steps after oxidation to 2’a and purification
by column chromatography.
transformations.14 Given the higher modularity of L8
compared to L7, several members of the Simplephos family
were evaluated next (See SI for details) and allowed for
identification of L9 as the best congener for the borylation of
1a (Entry 9). Further optimization of the solvent, temperature,
concentration, time and copper source led to a system which
afforded homoallylic boronate 2a as a single regioisomer
(
2a:3a >20:1) in 82% yield and 90% ee (Entry 10-15).
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neutral and electron-deficient aromatic substituents
participated well in the Cu-catalyzed borylation reaction,
delivering the product in moderate to good yield, good to
excellent regioselectivity and high enantioselectivity (2a’-2l’:
56-82% yield; chemoselectivity: 2.6:1 to >20:1; 86-91% ee).
Several functional groups (methoxy, fluoro, amino,
trifluoromethyl, chloro) are tolerated. Whereas a homoallylic
alcohol having a p-CN (2’n) substituent was isolated in much
reduced yield albeit in high ee, 2’o which displayed an alkyne
substituent was generated in high yield, chemo- and
enantioselectivity. Reduced performances were observed in
the borylation of heteroaromatic-containing 1,3-dienes
although satisfactory enantioinduction were still measured for
2’p and 2’r. Finally, skipped dienes 2’s-t – which derived from
the parent dendralenic 1,3-dienes – were isolated as single
regioisomers in good yield and high enantioselectivity.
Fig 3. Sequential borylation/oxidation of 2-alkyl substituted 1,3-
dienes. Reaction conditions: 1u-x (0.18-0.36 mmol), B2(pin)2
(0.15-0.30 mmol). Chemoselectivity assessed by 1H NMR after
borylation. Isolated yields for alcohols 2’v-x. Enantioselectivity
determined after oxidation by HPLC, GC, SFC using a chiral
a
stationary phase.
Conversion of non-separable isomers
Subsequently,
conjugated
2-alkyl-1,3-dienes
were
determined by 1H NMR (2’u+3’u). b At 0 °C for 24 h.
investigated (Fig. 3). Counter-intuitively – perhaps – the
reactivity, the chemoselectivity and the enantioselectivity
were all found to increase drastically when going from primary
The scope of the process was first evaluated for 2-(hetero)
aryl substituted 1,3-dienes. In most cases only products
resulting from 1,2- and 4,3-borylation were detected. The
selectivity was assessed by analysis of the crude reaction
mixture after borylation and the yields and enantiomeric
excess were measured after oxidation into the corresponding
homoallylic alcohols (20 examples, Fig. 2). Overall, most
conjugated 1,3-dienes containing electron-rich, electron-
(
(
1u-v), to secondary (1w) and finally tertiary alkyl substituents
1x). While primary and secondary alkyl favored 4,3-borylation,
a
sterically demanding 1-adamantyl group restored
preferential 1,2-borylation (7:1) generating 2’x in good yield
and excellent enantioselectivity. At first sight, these data
suggest that enantio-differentiation may preferentially occur
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Fig 6. Borylation/oxidation sequence of bis-diene 1z (0.36 mmol
scale). a 1,2-/4,3-selectivity = 10:1. b Inseparable mixture.
situation (S,S)-2’y was isolated in 86% yield and >20:1 dr with
(R,R)-L9. In the mismatch situation, the enantiomeric ligand
(S,S)-L9 proved able to substantially override the substrate
bias, generating (R,S)-2’y preferentially (85% yield; 1:7 dr). In
addition to serving as a prototype for further developments,
this example highlights the high chemoselectivity of our
protocol as only one of the four olefinic functionalities present
in (S)-1y underwent borylation.
Fig 4. Non-linear effect study. Reaction conditions: 1a (0.12
mmol), B2(pin)2 (0.10 mmol). Chemoselectivity >20:1 in all cases
as assessed by 1H NMR. Enantioselectivity determined after
oxidation by HPLC using a chiral stationary phase. Average of
two experiments.
Finally, double borylation of bis-diene 1z led preferentially
to the formation of (S,S)-2’z (>99% ee) over the meso isomer
(R,S)-2’z (8:1 dr) (Fig. 6). This approach is based on the Horeau
duplication principle and demonstrates that the catalyst can
induce high levels of selectivity of each diene moiety
independently of the other leading to an overall
amplification.19,20
Conclusions
In conclusion, we have developed a highly chemo-, regio- and
enantioselective Cu-catalyzed borylation of 2-aryl and 2-alkyl
substituted 1,3-dienes using a chiral phosphanamine ligand.
The method is compatible with a broad range of functional
groups and provides rapid access to synthetically relevant
homoallylic boronates/alcohols and is amenable to a catalyst-
controlled diastereoselective process. Further mechanistic
investigations into the origin of the selectivity of this catalytic
reaction are underway.
Fig 5. Catalyst-controlled diastereoselective borylation of (S)-1y.
Reaction conditions: (S)-1y (0.24 mmol), B2(pin)2 (0.20 mmol).
Chemoselectivity >20:1 in all cases as assessed by 1H after
borylation. Diastereoselectivity assessed by 1H and 13C{1H} NMR
after borylation and oxidation. Isolated yields after oxidation.
during 1,4-protodecupration from intermediate
during 1,2-borocupration as particularly congested
quaternary Cu- -allyl species would be formed in the case of
2’x. The situation is likely to be more subtle and complex.
Indeed, non-linear-effect studies revealed substantial
C rather than
Conflicts of interest
a
“There are no conflicts to declare”.
σ
B
a
Acknowledgements
deviation from linearity – a signature for catalyst aggregation
as is apparent from Fig. 4.15
This work was supported by the University of Geneva. S.
Rosset is acknowledged for technical assistance.
Catalyst-controlled diastereoselective transformations
where a chiral catalyst can install one (or several) new
stereocenter(s) independently of the stereochemical
complexity of the substrate have gained a certain momentum-
recently.16,17 Hence, the innate bias imposed by (S)-1y on the
Notes and references
a
University of Geneva, Department of Organic Chemistry, 30
quai Ernest Ansermet, 1211 Geneva-4, Switzerland.
Cu-catalyzed borylation was assessed using DrewPhos (L10
)
†
Electronic Supplementary Information (ESI) available:
leading to a 2:1 diastereomeric ratio in favor of (S,S)-2’y (Fig.
5).18 Diastereoselective borylation reactions were performed
with both enantiomers of the chiral ligand. In the match
Experimental procedures, characterization of all new
compounds and spectral data.
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