Formyl MIDA Boronate: C1 Building Block Enables Straightforward Access to α-Functionalized Organoboron Derivatives

Article abstract of DOI:10.1002/anie.202007651

Formyl MIDA boronate has been known to be an elusive type of acylboronate that has not been obtained to date. In this work, an approach to the one-pot preparation and chemical transformations of formyl MIDA boronate were developed to provide new types of

Full text of DOI:10.1002/anie.202007651

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Accepted Article
Title: Formyl MIDA Boronate: a C1 Building Block Enabling
Straightforward Access to α-Functionalized Organoboron
Derivatives
Authors: Yevhen M. Ivon, Ivan V. Mazurenko, Yuliya O. Kuchkovska,
Zoya V. Voitenko, and Oleksandr O Grygorenko
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10.1002/anie.202007651
Angewandte Chemie International Edition
RESEARCH ARTICLE
Formyl MIDA Boronate: a C1 Building Block Enabling
Straightforward Access to α-Functionalized Organoboron
Derivatives
Yevhen M. Ivon,[a,b] Ivan V. Mazurenko,[a,b] Yuliya O. Kuchkovska,[a,b] Zoya V. Voitenko,[b] and
Oleksandr O. Grygorenko*[a,b]
[a]
Yevhen M. Ivon, Ivan V. Mazurenko, Yuliya O. Kuchkovska, Dr. Oleksandr O. Grygorenko
Enamine Ltd.
Chervonotkatska Street 78, Kyiv 02094, Ukraine
Yevhen M. Ivon, Ivan V. Mazurenko, Yuliya O. Kuchkovska, Prof. Dr. Zoya V. Voitenko, Dr. Oleksandr O. Grygorenko
Taras Shevchenko National University of Kyiv
[b]
Volodymyrska Street 60, Kyiv 01601, Ukraine
E-mail: gregor@univ.kiev.ua
URL: www.enamine.net
Supporting information for this article is given via a link at the end of the document.
Abstract: Formyl MIDA boronate has been known to be an elusive
instance of acylboronate derivatives which could not be obtained to
date. In this work, an approach to one-pot preparation and chemical
transformations of formyl MIDA boronate was developed to provide
new structural types of α-functionalized organoboron compounds.
Among them are acylboronate reagents which present boron-
substituted analogues of ynones and β-dicarbonyl compounds. The
developed synthetic procedures utilizing formyl MIDA boronate were
demonstrated to be tolerant to diverse functional groups, which
makes this reagent an advantageous C1 building block for extending
the scope of organoboron chemistry.
Introduction
Continuous advancement of organoboron chemistry has an
enormous impact on enabling new chemical reactions and
extending the scope of accessible molecular scaffolds. Apart
from elaboration of synthetic methods which utilize C–B bond
transformation, development of new organoboron reagents
which allow to achieve greater structural diversity of the target
compounds presents another important objective.[1,2] Over the
last decade, lots of efforts were put into synthesis of α- and β-
functionalized boronates which were shown to be excellent
building blocks for modular construction of heterocyclic
compounds (Scheme 1, A).[3–12]
Among the mentioned boron-containing structural motifs,
acylboron derivatives (Scheme 1, B) are known to be an
emerging class of compounds with strong potential for novel
synthetic applications.[13] The first characterized acylboranes
contained either a diamine ligand coordinated to the B-atom
(type a)[14–16] or an N-heterocyclic carbene (type b).[17]
Development of acyltrifluoroborate reagents (type c)[18,19] was
another important contribution which allowed to elaborate a new
method of amide-forming ligation.[20–22]
One more significant advancement in acylboronate chemistry
was adaptation of N‐methyliminodiacetyl (MIDA) boryl group
(type d, Scheme 1, B).[6–9,23–28] Selection of MIDA as a ligand
enabled the preparation of acyl boronates by oxidation reactions
and made the resulting boronic reagents compatible with diverse
Scheme 1. Application of α- and β-functionalized boronates as reagents for
modular construction of heterocyclic scaffolds (A), previously reported
structural types of acylboranes (B).
1
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10.1002/anie.202007651
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RESEARCH ARTICLE
functional transformations and heterocyclizations. Similarly to
acyltrifluoroborate salts (type c), MIDA substituted acylboranes
were also shown to undergo amide-bond forming ligations and
allowed to extend the scope of compatible hydroxylamine
substrates for this method.[23] Besides, application of MIDA
boronate functionality was favourable for the synthesis of
carboxy MIDA boronate.[29] This novel C1 building block allowed
accessing carbamoyl- and thiocarboboronate derivatives, which
were also used in heterocyclization reactions.
The aforementioned utility of acylboron compounds prompted us
to develop a novel approach to the in situ synthesis of formyl
MIDA boronate
1
starting from the readily available
hydroxymethyl MIDA boronate 2. The reactivity of 1 and its
application for modular construction of new boronate-containing
functional moieties and heterocyclic derivatives are covered in
this work (Scheme 2, B).
Despite the growing interest in new organoboron reagents,[1–3]
the preparation of another C1 building block – formyl MIDA
boronate 1 remained unachieved to date. According to the
literature, attempts to obtain 1 by oxidation of alcohol 2 with
Dess–Martin periodinane (DMP)[28] and by vicinal diol 3 cleavage
Results and Discussion
Our initial attempts to perform oxidation of alcohol 2 with DMP,
PCC, or DMSO – (COCl)2 (Swern reaction) in various solvents
were unsuccessful. Due to the low solubility of 2 in CH2Cl2 and
toluene, which are typically used as solvents for the Swern
oxidation, a mixture of CH3CN – DMSO (9:1) was used (Scheme
3). Under these conditions, the typical 90–98% conversion of 2
into formylboronate 1 was found to be reproducible (according to
1H NMR; the measurements were done for three separate
experiments). Since the product 1 appeared to be unstable
towards concentration of its solution (see the Supporting
information), a possibility of its use as a solution (containing also
less than 10% of thioacetal by-product 9) in one-pot reaction
sequences was further evaluated. Unfortunately, our attempts to
convert 1 into is trifluoroborate derivative were unsuccessful.
The origin of strikingly different stability of formyl MIDA boronate
1 and its previously described analogue 5 (which was even
characterized crystallographically) is of particular interest.
Similar values of 13C NMR chemical shifts of the carbonyl groups
of 1 (235.6 ppm in CD3CN–DMSO-d6 (9:1)) and 5 (233.1 ppm in
CD2Cl2)[30] indicate that the electronic effects of the correspond-
ing boron-containing substituents might be more or less similar.
Therefore, we suggest that the main cause of the remarkable
stability of 5 as compared to MIDA boronate 1 is the increased
steric hindrance introduced by the C6F5 and pyridine
substituents at B-atom which presumably shield carbonyl group
from the nucleophilic attack and prevent spontaneous polyme-
rization (see Figure S1 for the X-ray structure of 5). On the
contrary, the B-atom of 1 is coordinated to the conformationally
constrained tridentate ligand (MIDA) which significantly
increases the accessibility of carbonyl moiety of formyl boronate
and enhances its reactivity (see Figure S2 for the X-ray
structures of some acyl MIDA boronates).
[25]
with NaIO4 both led to formyl MIDA borate 4 (Scheme 2, A).
The successful isolation of formylboronate derivatives could be
only achieved for frustrated Lewis pairs.[30–37] Among the known
examples, compounds 5–8 (Figure 1) were generally synthe-
sized by a catalyzed reaction of either HB(C6F5)2 or B(C6F5)3
with CO.[30–35] It should be noted that isolation of a similar
formyliminium derivative was possible for it trifluoroborate salt.[38]
Several typical reactions of aldehydes were tested with the
substrate 1 (Scheme 3). In particular, Wittig olefination of 1 with
a stabilized phosphonium ylide gave 10 in 68% yield over 2
steps. Condensation with N-nucleophiles including TsNHNH2
and BnONH2 led to 11 and 12 in 74% and 46% yield,
Scheme 2. Previous unsuccessful attempts to synthesize formyl MIDA
boronate (A), and the main results of this work (B).
respectively. Reductive amination of
1 with mono- and
disubstituted amines afforded α-amino MIDA boronates 13a–d
with 37–71% yield.[39] The preparation of dithioacetal 14 from 2
using 1,3-propane dithiol for the second reaction step appeared
to be less efficient (28% yield). Synthesis of acetals 15a and 15b
using either neopentyl glycol or trimethyl orthoformate was
achieved from 2 in 52% and 38% yield, respectively.
The addition of organometallic reagents to the carbonyl moiety
of 1 is another class of reactions that can be especially useful for
the generation of polyfunctional synthetic intermediates.
Because 1 was available as a solution in CH3CN, the use of
reagents with high basicity should be avoided. Nevertheless,
treatment of 1 with PhMgCl resulted in alcohol 16, which was
Figure 1. Previously reported formylboron derivatives.
2
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10.1002/anie.202007651
Angewandte Chemie International Edition
RESEARCH ARTICLE
isolated in 36% yield over 2 steps. Yet, more basic reagents (RLi
and alkyl-MgCl) were not compatible with the aforementioned
reaction conditions.
complex mixture of products, whereas the reaction of
phenylacetyl bromide (20b) gave target compound 21b along
with elimination product 22b which could not be separated.
Addition of alkyl zinc reagents to 1 in the presence of Lewis acid
additives led to the formation of the complex reaction mixtures
1
containing less than 40% of the target products (according to H
NMR spectra, see the Supporting Information). Nevertheless,
the reaction of 1 with allylzinc reagents which were generated in
situ from allyl bromides 17 in the presence of Cp2TiCl2 as a
catalyst[40] was found to be efficient for the preparation of
homoallylic alcohols 18a–e with up to 57% yield over 2 steps
(Scheme 4). Similarly, propargyl bromide (17f) could be
subjected to the same reaction conditions to provide
homopropargyl alcohol 18f in 38% yield. In contrast, the reaction
with 1-bromobut-2-yne (17g) proceeded with rearrangement and
led to allene 19g. However, isolation of pure compound 19g
could not be achieved due to its instability. The addition of
organozinc reagent derived from (3-bromoprop-1-yn-1-
yl)benzene (17h), in turn, gave an inseparable mixture of 18h
and 19h (60:40) in 45% yield.
Scheme 4. Addition of organozinc reagents to 1 catalyzed by Cp2TiCl2.
Since alkyl iodides should be more reactive in similar
transformations,[40] n-propyl iodide, isopropyl iodide, and Boc-3-
iodo-L-alanine methyl ester were tested under the
aforementioned conditions; in all cases, unidentified products
were formed.
Scheme 3. Synthesis of formyl MIDA boronate (1) and its reactions with
typical nucleophiles (the yields are given for two steps)
To achieve the preparation of more diverse α-hydroxyboronates,
other organometallic reagents were tested. Organotitanium
reagents were expected to provide the best balance between
Unfortunately, the application of the aforementioned method to
α-bromocarbonyl compounds (i.e. Reformatsky-type reactions)
was not effective. The reaction of ester derivative 20a resulted in
3
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10.1002/anie.202007651
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RESEARCH ARTICLE
nucleophilicity and basicity in further transformations.[41] First,
the addition of several sp3- and sp2-hybridized derivatives 23 to
1 was examined (Scheme 5). Whereas the reaction with 23
derived from n-BuLi appeared to be low-yieding (8% for 24a),
the use of PhMgCl – ClTi(Oi-Pr)3 allowed improving the yield of
16 up to 53% as compared to reaction with the simple Grignard
reagent (36%, Scheme 3). However, the method did not work
well with vinyl magnesium chloride and led to a complex mixture
of products instead of 24b.
allowed to suppress formation of by-products significantly and
avoid elimination of H2O from the final product 32a (Scheme 7).
Therefore, deprotonation of ketones 29a–d and esters 29e,d
was carried out with LDA at –78 to –70 C, and further reaction
of enolates 30 with 1 provided aldol adducts 31 in 39–60% yield.
Scheme 5. The addition of organotitanium reagents derived from n-BuLi,
PhMgCl, and CH2=CHMgCl to 1.
Next, the addition of alkynyl carbanions to 1 was studied
(Scheme 6). In this case, organotitanium reagents 25 generated
from terminal alkynes 26 via deprotonation with n-BuLi followed
by transmetallation were used to access unprecedented α-
hydroxy propargyl boronates 27.[42] The reaction of 1 with 25a–c
obtained from t-Bu-, Me3Si- and Ph-substituted acetylenes
proceeded smoothly to give propargyl alcohols 27a–c in 60–
89% yield from 2. Importantly, the selected method displayed
high tolerance to diverse functional groups including benzyl
ether (27d, 76% yield), chloride (27e, 64%), nitrile (27f, 28%),
Boc-protected amine (27g, 76%), and cyclopropane ring (27i,
59%). Synthesis of alcohol 27h from 3,3-diethoxy-1-propyne
was achieved only with a 20% yield according to 1H NMR
spectra, but the isolation of the target product was not
successful due to its instability and complicated purification.
Limitations of the method included the use of parent acetylene
and alkynes bearing an ester moiety. It should be noted that
several products 27 were noticed to undergo gradual oxidation
into acetoxyboronates 28 upon column chromatography,
recrystallization, or storage on air and thus should be used
immediately after purification.
Scheme 6. Addition of organotitanium reagents to 1.
Another type of studied transformations was addition of enolates
to 1, i.e. aldol reaction (Scheme 7). In order to find the best
reaction conditions, we first screened effectiveness of using
Ti(IV)-, Zn- and Li-enolates using cyclohexanone (29a) as a
model substrate. Generation of the Ti(IV)-enolate using
ClTi(Oi-Pr)3 resulted only in minor quantities of the crude target
product. Although utilization of Zn-enolates allowed us to
achieve moderate yields, the final compound was formed along
with the H2O elimination product and considerable amount of
other by-products. On the other hand, the use of Li-enolate
In addition, the reaction of 1 with deprotonated benzyl cyanide
was also examined and gave 32 with 41% yield as ca. 1:1
mixture of diastereomers.
Due to wide application of ynones[43,44] and 1,3-dicarbonyl
compounds[45–47] in synthetic organic chemistry, we next aimed
at the chemoselective oxidation of α-hydroxy boronates, which
allowed synthesis of boron-substituted analogues of ynones and
β-dicarbonyl compounds for the first time (Scheme 8). Dess–
Martin oxidation was adapted for the preparation of 33–36 by
using the CHCl3–CH3CN (9:1) as the solvent to ensure good
4
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10.1002/anie.202007651
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RESEARCH ARTICLE
solubility of the starting alcohols (conditions A). In most cases,
oxidation of alcohols 27 was achieved with the high conversion,
however, isolated yields of the purified products were somewhat
decreased due to their limited stability on silica gel. As a result,
the isolated yields for ynones 33 ranged from 10% to 76%. In
several cases when the aforementioned procedure was
In summary, synthesis and chemical reactions of formyl MIDA
boronate were described for the first time. Because this reagent
could not be isolated due to its instability, protocols relying on
utilization of formyl MIDA boronate in one-pot transformations
were elaborated. Swern oxidation of hydroxymethyl MIDA boro-
nate followed by addition of C-, N-, O-, or S-nucleophiles provide
straightforward access to α-functionalized boronic acid derivati-
Scheme 7. Addition of lithium enolates 30 to 1.
unsuccessful or low-yielding, the Swern oxidation protocol was
applied as an alternative (conditions B).
In contrast, oxidation of aldols 31 appeared to be more efficient,
mainly because of the higher stability of final compounds 34. In
this case, products 34a–f were obtained in the enol form (except
34e) in 61–92% yield. Yet, the application of neither Dess –
Martin nor Swern oxidation conditions was fruitful for the
preparation of 35 from 32. Similarly, oxidation of α-hydroxy
homoallyl and homopropargyl MIDA boronates 18a,b,f could be
achieved by neither method. The only successful α-hydroxy
homoallyl MIDA boronate oxidation was carried out for non-
enolizable acylboronate 36c from 18c (91% for conditions A,
67% for conditions B).
Finally, one of the potential applications of newly synthesized
acylboronates was demonstrated by heterocyclizations of 34
with N2H4 (Scheme 9). The following reactions demonstrate the
facile construction of pyrazole boronic acid derivatives which can
be used as building blocks for the synthesis of agrochemicals
Scheme 8. Oxidation of alcohols obtained in this work into ynones 33, 1,3-
dicarbonyl compounds 34, and other important synthetic derivatives.
and pharmaceutical agents.[48–51] As
a result, acyl MIDA
boronates 34c and 34d reacted with high 88% and 56% yield,
respectively, to give 3,5-disubstituted 1H-pyrazoles 37c,d.
Conclusion
Scheme 9. Heterocyclizations of 34c,d.
5
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10.1002/anie.202007651
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ves. In general, the proposed reaction conditions were
compatible with diverse functional moieties and led to target
products in moderate to high yield. Among the obtained compo-
unds, previously unprecedented α-hydroxy propargyl MIDA
boronates, alkyne-substituted acylboronates, and β-dicarbonyl
MIDA boronates provide new opportunities for modular
construction of complex scaffolds and heterocycles, which was
demonstrated by the preparation of pyrazole-derived MIDA
boronates. Moreover, the obtained acyl boronates are potentially
advantageous for conjugation by amide-bond forming
ligations.[23]
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The work was funded by Enamine Ltd. O.O.G., Y.M.I. and Z.V.V.
were also funded by Ministry of Education and Science of
Ukraine (O.O.G.: Grant No. 19BF037-03; Y.M.I. and Z.V.V.:
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10.1002/anie.202007651
Angewandte Chemie International Edition
RESEARCH ARTICLE
Entry for the Table of Contents
Organoboron chemistry
One-pot preparation and chemical reactions of formyl MIDA boronate were described in this work. The developed methods provide
new structural types of α-functionalized organoboron compounds including boron-substituted analogues of ynones and β-dicarbonyl
compounds. The proposed synthetic procedures demonstrate high tolerance to diverse functional moieties, which makes formyl
MIDA boronate an advantageous C1 building block for extending the scope of organoboron chemistry.
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