Uncatalyzed Carboboration of Seven-Membered-Ring trans-Alkenes: Formation of Air-Stable Trialkylboranes

Article abstract of DOI:10.1021/jacs.7b03986

Seven-membered-ring trans-alkenes undergo rapid, uncatalyzed carboboration reactions to form trialkylboranes as single diastereomers. In contrast with other trialkylboranes, which can ignite in the presence of oxygen, these trialkylboranes are stable in air. Hindered trialkylboranes can undergo reverse hydroboration reactions to form allylic silanes or can be oxidized to afford highly substituted triols. This reaction sequence permits the construction of compounds with up to five consecutive stereocenters. Control experiments and computational studies support a concerted mechanism for the migratory insertion of the alkene into the carbon-boron bond, similar to the mechanism for hydroboration.

Full text of DOI:10.1021/jacs.7b03986

Communication
Uncatalyzed Carboboration of Seven-Membered-Ring
trans-Alkenes: Formation of Air-Stable Trialkylboranes
Jillian R. Sanzone, Chunhua Tony Hu, and Keith A. Woerpel
J. Am. Chem. Soc., Just Accepted Manuscript • Publication Date (Web): 01 Jun 2017
Downloaded from http://pubs.acs.org on June 2, 2017
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Uncatalyzed Carboboration of Seven-Membered-Ring trans-Alkenes:
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Formation of Air-Stable Trialkylboranes
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Jillian R. Sanzone, Chunhua (Tony) Hu, and K. A. Woerpel
Department of Chemistry, New York University, 100 Washington Square East, New York, NY 10003 United States
Supporting Information Placeholder
membered ring transition state similar to the widely used
hydroboration reaction. The resulting boranes can be
oxidized with retention of configuration to form triols
with five consecutive stereocenters.
ABSTRACT: Sevenꢀmemberedꢀring transꢀalkenes unꢀ
dergo rapid, uncatalyzed carboboration reactions to form
trialkylboranes as single diastereomers. In contrast with
other trialkylboranes, which can ignite in the presence of
oxygen, these trialkylboranes are stable in air. Hindered
trialkylboranes can undergo reverse hydroboration reacꢀ
tions to form allylic silanes or can be oxidized to afford
highly substituted triols. This reaction sequence permits
the construction of compounds with up to five consecuꢀ
tive stereocenters. Control experiments and computaꢀ
tional studies support a concerted mechanism for the
migratory insertion of the alkene into the carbon–boron
bond, similar to the mechanism for hydroboration.
Initial experiments indicated that an alkene can react
with a trialkylborane provided the alkene is sufficiently
strained. transꢀAlkene 1, which can be prepared from
1
0
1,3ꢀpentadiene, a silylene source, and benzaldehyde,
reacted with triethylborane in the absence of any catalyst
to form borane 2 in 92% isolated yield in under two
hours (eq 1). A single stereoisomer of a new product
was formed, with three new ethyl resonances present in
1
the H NMR spectrum. The structure was tentatively
assigned as 2.
The reactions of organoboranes are powerful transforꢀ
1
mations in synthetic organic chemistry. For example,
the hydroboration of alkenes, the stereospecific and ofꢀ
ten stereoselective addition of a boron–hydrogen bond
across a carbon–carbon double bond, is a commonly
used transformation for adding the elements of water to
Several properties of 2 contrasted with the properties
associated with trialkylboranes. Compound 2 was found
to be stable to column chromatography and air, comꢀ
pared to most trialkylboranes, which react explosively
with oxygen. Attempts to make Lewis acidꢀbase comꢀ
plexes with ammonia, triethylamine, and trimeꢀ
thylphosphine, or to form borates with cesium fluoride
and sodium azide, were also unsuccessful. The
NMR chemical shift of δ 32.1 ppm for borane 2 was
dramatically different from chemical shifts of other triꢀ
2
3
unsaturated substrates. The addition of boron–oxygen,
4
5
boron–nitrogen, and boron–carbon bonds across the
carbon–carbon triple bond of alkynes have also been
reported, and recently catalystꢀfree 1,2ꢀcarboborations of
diarylchloroboranes and diarylborinium ions with alꢀ
9
6
kynes was observed. The corresponding reaction of
11
B
boron–carbon bonds with alkenes is considerably more
difficult. Metalꢀcatalyzed variants of this reaction have
7
been reported, but little progress has been made in deꢀ
11
alkylboranes (δ 80–90 ppm). The large upfield shift is
more consistent with a Lewis acidꢀbase complex where a
heteroatom coordinates to a trialkylborane.
veloping a metalꢀfree carboboration using simple trialꢀ
8
kylboranes.
12
Here, we report that the uncatalyzed synꢀaddition of
trialkylboranes to sevenꢀmemberedꢀring transꢀalkenes
occurs at room temperature in high yields and with high
diastereoselectivity. The resulting hindered boranes are
airꢀstable, unlike most trialkylboranes, which are pyroꢀ
The unusual properties of borane 2 led us to conduct
additional experiments to confirm the structure. When a
solution of trialkylborane 2 in C D was heated to 80 °C
in a sealed tube with nꢀbutylamine, cisꢀalkene 3 and
aminoborane 4 were formed in 95% and 85% yields,
6
6
9
phoric. Analysis of singleꢀcrystal Xꢀray crystallographic
1
respectively, as determined by H NMR spectroscopic
analysis (Scheme 1). Hydrogen gas was also observed
studies gives insight into the unique stability of these
compounds. Mechanistic studies indicate that the carꢀ
boboration reaction occurs through a concerted, fourꢀ
(δ 4.43 ppm). Formation of aminoborane 4 and hydroꢀ
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gen gas indicate that a diethylboryl group and a hydroꢀ
gen atom were removed from product 2. The elimination
occurred only slowly at room temperature (6% alkene
formation after 19 h), so these mixtures were heated (80
pounds. The methyl and ethyl substituents on C2 and
C4, respectively, block access to the empty orbital on the
boron atom. These groups also prevent free rotation
around the C3–B1 bond, forcing trialkylborane 2 to
adopt the conformer shown in the Xꢀray crystal structure
(Figure 1).
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°C) to give rapid and clean conversions (95%). Typicalꢀ
ly, trialkylboranes require high temperatures (> 200 °C)
13
for dehydroboration.
Hyperconjugation of adjacent bonds also contribute to
the stability of trialkylborane 2. The bond angles of the
methylene carbons attached to the boron atom are closer
to sp hybridization (C16ꢀC15ꢀB1 = 119.08 (13)° and
C18ꢀC17ꢀB1 = 120.62 (15)°) than sp hybridization. The
Scheme 1. Dehydroboration of Trialkylborane 2
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B1–C15 and B1–C17 bond lengths (1.570 (2) Å and
1.574 (2) Å) are shorter than the B1–C3 bond length
(1.6042 (18) Å) and shorter than typical carbon–boron
1
6
bond lengths (1.60 Å). The large bond angles and short
bond lengths are likely the result of the filled orbitals of
the methylene groups on C15 and C17 donating electron
density into the empty orbital on the boron atom, further
1
7
adding to the stability of trialkylborane 2. The donaꢀ
tion of electron density from the α–C–H bonds due to
the locked conformation of borane 2, and donation of
11
The reaction of compound 2 with an alkene further
confirmed the structure (Scheme 1). Heating borane 2 in
the presence of allylbenzene 5 yielded trialkylborane 6
other nearby bonds, likely account for the unusual
NMR chemical shift.
B
18
Table 1. Substrate Scope of Carboboration
(
74%) and cisꢀalkene 3 (96%). This alkylborane had a
11
B NMR chemical shift of δ 85.9 ppm, which is conꢀ
sistent with product 6 having a diethylboryl functional
group.
11, 14
The results shown in Scheme 1 would not be
consistent if new carbon–boron and carbon–carbon
bonds were not formed during the original carboboration
reaction (eq 1).
Figure 1. Molecular structure of trialkylborane 2 (ellipꢀ
soids set at 50% probability). The hydrogen atoms, except
those on C1–C5, have been removed for clarity.
Eventually, crystals suitable for Xꢀray diffraction
studies were obtained to confirm the structure and give
insight into the unusual stability of 2. The stereochemiꢀ
cal configuration of this product is consistent with synꢀ
addition of the carbon–boron bond across the carbon–
carbon double bond, as observed for hydroboration. The
stability of trialkylborane 2 towards oxygen and Lewis
bases is likely a result of steric protection, a characterisꢀ
tic that allows isolation of unstable and reactive comꢀ
a
b
Isolated yields based on transꢀalkene. Unpurified yield:
the carbon–boron bond was oxidized to obtain a yield over
two steps (see Supporting Information).
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The synꢀcarboboration is general for a number of
regioisomeric products. Furthermore, such a radical
would not be configurationally stable, so products could
be formed as mixtures of stereoisomers. Only a single
stereoisomer was observed in the reactions of trialkylꢀ
boranes and transꢀalkenes, however. These results are
1
transꢀalkenes (Table 1). Aryl, alkenyl, and alkyl groups
were tolerated under the reaction conditions. In all casꢀ
es, addition was completely stereoselective and regioseꢀ
lective. If two alkene functional groups were present,
carboboration only occurred on the strained double bond
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more consistent with a concerted mechanism.
(
i.e., 10 and 13). Trialkylboranes containing five conꢀ
A stepwise pathway involving a zwitterionic intermeꢀ
2
5
secutive stereocenters (16) can be synthesized with
complete control of diastereoselectivity in each step.
Additionally, triethylborane or triꢀnꢀbutylborane can be
used as the borane source. Preliminary results show that
any unpurified trialkylborane derived from the hydroboꢀ
ration of an alkene will be tolerated, as illustrated by the
diate is also possible (Figure 2, III), but several factors
are inconsistent with this mechanism. Formation of βꢀ
silyl carbocations similar to III have resulted in nucleoꢀ
philic attack of the ring oxygen on the carbocation and
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rearrangement to form five–membered ring products.
No such rearrangement products were observed in the
carboboration reactions. A stepwise mechanism should
also allow trisubstituted alkenes to undergo carboboraꢀ
tion because these transꢀalkenes react rapidly with hinꢀ
19
formation of borane 18.
The 1,2ꢀcarboboration of alkenes is sensitive to steric
effects and strain. Alkenes with tertiary allylic carbon
atoms did not react with triethylborane. Trisubstituted
transꢀalkenes were also too hindered to react with triꢀ
ethylborane. Sterically demanding trialkylboranes could
not be used: no reaction was observed between 1 and triꢀ
2
0b
dered electrophiles in a stepwise fashion. Trisubstitutꢀ
ed alkenes were unreactive with triethylborane, however.
Additionally, a zwitterionic, stepwise mechanism imꢀ
plies that nucleophilicity of the alkene is an important
factor for carboboration to occur. When nucleophilic
2
0
secꢀbutylborane. A strained transꢀcyclooctene reacted
only slowly with triethylborane, indicating the extent to
enamines, which should be more nucleophilic than a
21
20b, 27
which strain is important for reactivity.
strained allylic silane,
were subjected to the carꢀ
boboration reaction, no reaction was observed. This
observation is inconsistent with a stepwise mechanism
involving zwitterionic intermediates. Taken together,
these data are more consistent with a concerted mechaꢀ
nism similar to the mechanism for hydroboration.
Given that the uncatalyzed migratory insertion of an
alkene into the carbon–boron bond is unprecedented,
efforts were made to provide insight into the reaction
mechanism. Three mechanisms for the carboboration
reaction were considered. One possible mechanism has
a fourꢀcentered transition state resembling the mechaꢀ
nism of the hydroboration of alkenes (Figure 2, I). Alꢀ
ternatively, stepwise pathways involving a radical (Figꢀ
ure 2, II) or a zwitterion (Figure 2, III) are possible.
Computational studies also support a concerted
mechanism. Model structures of the starting materials
and possible transition states were investigated using
21
density functional methods (M06ꢀ2X/6ꢀ311+G(2d,p)).
2
8
A lowꢀenergy fourꢀmembered transition state involving
concerted addition of a carbon–boron bond to the carꢀ
bon–carbon double bond (i.e., synꢀcarboboration) was
found for addition to a transꢀoxasilacycloheptene related
to 1 (about 3 kcal/mol). In contrast, for an unstrained
alkene (ethylene), the synꢀcarboboration transition state
was over 20 kcal/mol higher in energy than the starting
materials. The computational results were also conꢀ
sistent with the regioselectivity observed: the transition
state leading to the observed isomer was 5 kcal/mol
lower in energy than the transition state with the other
regiochemistry. Efforts to identify intermediates along a
stepwise pathway led only to highꢀenergy structures.
Figure 2. Possible transition state and intermediates of carꢀ
boboration reaction.
Several experiments provide evidence against a
mechanism involving radicals. A radical mechanism
would likely include intermediate II, a free radical that
would react rapidly with other radicals. In the presence
22
of a radical trap (TEMPO), the reaction proceeded
The carbon–boron bond and carbon–silicon bonds
can be oxidized to yield synthetically useful products.
Oxidation of the carbon–boron bond in trialkylborane 2,
followed by baseꢀmediated rearrangement, formed oxꢀ
smoothly, and no additional products were observed.
Furthermore, crossover experiments provide evidence
against a mechanism where the boron atom and alkyl
group are separated (intermediate II). Carboboration of
transꢀalkene 1 in the presence of a mixture of triethylꢀ
borane and triꢀnꢀbutylborane afforded only products
29
asilacyclopentane 19 in 66% yield over two steps.
Oxidation of the carbon–silicon bond, using conditions
3
0
optimized for hindered silyloxy groups, yielded triol
20. Previously reported routes to synthesize a product
with a similar substitution pattern were longer, with
2
1
where all three alkyl groups were identical (2 and 7).
Additionally, stabilization of a βꢀsilyl radical is small (1
2
3
31
kcal/mol). As a result, both γꢀ and βꢀsilyl radicals
some steps proceeding with low diastereoselectivity.
should form as intermediates, leading to a mixture of
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. Hirner, J. J.; Faizi, D. J.; Blum, S. A. J. Am. Chem. Soc. 2014,
Scheme 2. Oxidation of Carbon–Boron and Carbon–
Silicon Bonds
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136, 4740.
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0
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Ed. 2015, 54, 5228.
8. Ene reactions of allylboranes with alkenes have been reported to
proceed by sixꢀmembered ring transition states: a) Singleton, D. A.;
Waller, S. C.; Zhang, Z.; Frantz, D. E.; Leung, S.ꢀW. J. Am. Chem.
Soc. 1996, 118, 9986; b) Frantz, D. E. and Singleton, D. A. Org. Lett.
In conclusion, the synꢀcarboboration of alkenes, altꢀ
hough not generally observed during synꢀhydroboration,
is an equally viable reaction. The resulting trialkylꢀ
boranes were formed as single diastereomers, and up to
five consecutive stereocenters can be formed in a few
synthetic steps. The product’s carbon–boron and carꢀ
bon–silicon bonds can be oxidized to form synthetically
useful triols.
1
999, 1, 485.
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2014, 33, 4251.
1
1
1
1
4. Oxidation of trialkylborane 6 provided 3ꢀphenylꢀ1ꢀpropanol,
ASSOCIATED CONTENT
which would be expected from the hydroboration and subsequent
oxidation of allylbenzene (5): details are provided as Supporting
Information.
15. Hertz, V. M.; Ando, N.; Hirai, M.; Bolte, M.; Lerner, H.ꢀW.;
Yamaguchi, S.; Wagner, M. Organometallics 2017, DOI:
10.1021/acs.organomet.6b00800.
The Supporting Information is available free of charge on
the
ACS
Publications
website.
Experimental procedures, stereochemical proofs, Xꢀray
data, and full characterization (PDF)
Xꢀray crystallographic data for 2 (CIF)
1
6. Allen, F. H.; Kennard, O.; Watson, D. G. J. Chem. Soc., Perkin
Trans. 2 1987, S1.
7. Boese, R.; Bläser, D.; Niederprüm, N.; Nüsse, M.; Brett, W. A.;
1
Xꢀray crystallographic data for entꢀ10 (CIF)
Schleyer, P. v. R.; Bühl, M.; Hommes, N. J. R. v. E. Angew. Chem.
Int. Ed. Engl. 1992, 31, 314.
AUTHOR INFORMATION
Corresponding Author
1
8. Natural bond orbital calculations also indicate that nearby
carbon–hydrogen and carbon–carbon bonds interact with the empty
p orbital on the boron atom. These contribute to the increased
2
*kwoerpel@nyu.edu
stability of 2 compared to other trialkylboranes. Details are provided
as Supporting Information.
19. The use of triphenylborane or dibutylboron triflate resulted in
decomposition.
Notes
The authors declare no competing financial interest.
2
0. (a) Taylor, M. T.; Blackman, M. L.; Dmitrenko, O.; Fox, J. M.
J. Am. Chem. Soc. 2011, 133, 9646; (b) Sanzone, J. R.; Woerpel, K.
A. Angew. Chem. Int. Ed. 2016, 55, 790.
ACKNOWLEDGMENTS
2
1. See Supporting Information for details.
This research was supported by the National Science Founꢀ
dation (CHEꢀ1362709). J.R.S. was supported by a Margaꢀ
ret Strauss Kramer Fellowship from the NYU Department
of Chemistry. K.A.W. thanks the Global Research Initiaꢀ
tives, NYU and NYU Florence, for a fellowship. NMR
spectra were acquired with the TCI cryoprobe and Bruker
Advance 400 were supported by the National Institutes of
Health (OD016343) and the National Science Foundation
22. Taniguchi, T.; Sugiura, Y.; Zaimoku, H.; Ishibashi, H. Angew.
Chem. Int. Ed. 2010, 49, 10154.
2
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Tetrahedron Lett. 1971, 48, 4597.
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7. Mayr, H.; Kempf, B.; Ofial, A. R. Acc. Chem. Res. 2003, 36,
8
2
2
2
2
66.
(
CHEꢀ01162222), respectively. We thank Dr. Chin Lin for
his assistance with NMR spectroscopy and mass spectromꢀ
etry. C.H. thanks the support from the Materials Research
Science and Engineering Center (MRSEC) program of the
National Science Foundation (NSF) under Award Numꢀ
bers DMRꢀ0820341 and DMRꢀ1420073.
28. Brown, H. C.; Zweifel, G. J. Am. Chem. Soc. 1960, 82, 4708.
29. Direct oxidation of the boron atom in 2 without rearrangement
leads to the sevenꢀmemberedꢀring alcohol.
3
0. Smitrovich, J. H.; Woerpel, K. A. J. Org. Chem. 1996, 61,
044.
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To format doubleꢀcolumn figures, schemes, charts, and tables, use the following instructions:
Place the insertion point where you want to change the number of columns
From the Insert menu, choose Break
Under Sections, choose Continuous
Make sure the insertion point is in the new section. From the Format menu, choose Columns
In the Number of Columns box, type 1
Choose the OK button
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Now your page is set up so that figures, schemes, charts, and tables can span two columns. These must appear at the top of
the page. Be sure to add another section break after the table and change it back to two columns with a spacing of 0.33 in.
Table 1. Example of a Double-Column Table
Column 1
Column 2
Column 3
Column 4
Column 5
Column 6
Column 7
Column 8
Authors are required to submit a graphic entry for the Table of Contents (TOC) that, in conjunction with the manuscript title,
should give the reader a representative idea of one of the following: A key structure, reaction, equation, concept, or theorem,
etc., that is discussed in the manuscript. Consult the journal’s Instructions for Authors for TOC graphic specifications.
Insert Table of Contents artwork here
ACS Paragon Plus Environment