Enantioselective anti- And syn-(borylmethyl)allylation of aldehydes via br?nsted acid catalysis

Article abstract of DOI:10.1021/acs.orglett.0c03366

The enantioselective anti- and syn-(borylmethyl)allylation of aldehydes via phosphoric acid catalysis is reported. Both (E)- and (Z)-γ-borylmethyl allylboronate reagents were prepared via the Cu-catalyzed highly stereoselective protoboration of 1,3-dienyl

Full text of DOI:10.1021/acs.orglett.0c03366

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Letter
Enantioselective anti- and syn-(Borylmethyl)allylation of Aldehydes
via Brønsted Acid Catalysis
Jiaming Liu and Ming Chen*
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ABSTRACT: The enantioselective anti- and syn-(borylmethyl)allylation of aldehydes via phosphoric acid catalysis is reported. Both
(E)- and (Z)-γ-borylmethyl allylboronate reagents were prepared via the Cu-catalyzed highly stereoselective protoboration of 1,3-
dienylboronate. Chiral phosphoric acid-catalyzed aldehyde allylation with either the (E)- or (Z)-allylboron reagent provided 1,2-anti-
or 1,2-syn-adducts in good yields with high enantioselectivities. The application to the synthesis of morinol D was accomplished.
hiral nonracemic 1,2-anti- and 1,2-syn-2-hydroxymethyl-
3-ene-1-ols (highlighted in blue in Figure 1) are key
variant of this method was disclosed by the Shibasaki group.6
Using a cyclic carbonate as the allyl donor, Krische and co-
workers reported an elegant Ir-catalyzed anti-(hydroxymethyl)-
allylation strategy to access enantioenriched diol 1 (eq 2,
Scheme 1).7 By contrast, asymmetric synthesis of 1,2-syn-
isomer 2 mainly relies on vinyl Grignard addition to
enantioenriched epoxy alcohols (eq 3, Scheme 1).8 The
development of catalytic methods that allow for the access to
enantioenriched syn-isomer 2 would be desirable.
C
Pioneered by the Antilla group, chiral phosphoric acid-
catalyzed enantioselective aldehyde addition with unsaturated
organoboron compounds has emerged as a powerful method
to access enantioenriched homoallylic, allenic, and homo-
propargylic alcohols.9−12 Inspired by prior studies, we
envisioned a chiral phosphoric acid-catalyzed asymmetric
aldehyde allylboration strategy to synthesize both 1,2-anti-
and 1,2-syn-2-hydroxymethyl-3-ene-1-ols, 1 and 2, respectively.
As shown in Scheme 1, on the basis of the well-established
chairlike transition state typically involved in allylboration
chemistry,13 we anticipate that chiral phosphoric acid (R)-A-
catalyzed aldehyde addition with (E)-γ-borylmethyl allylboro-
nate 3 should provide 1,2-anti adduct 5 with high diastereo-
and enantioselectivity. Similarly, the reaction with (Z)-reagent
4 should generate 1,2-syn adduct 6 selectively. Subsequent
Figure 1. Selected natural products containing 1,2-syn- or anti-
hydroxymethyl-1,3-diols.
structural motifs in numerous biologically active natural
products.1−3 The diastereo- and enantioselective synthesis of
these structural entities is therefore an important objective in
organic synthesis. Several approaches are available to generate
these molecules in a racemic form with good anti- or syn-
selectivities.4 However, methods that allow for their
enantioselective syntheses are underdeveloped. As shown in
Scheme 1, Evans reported a chiral auxiliary-based aldol
addition/reduction reaction sequence to generate enantioen-
riched 1,2-anti-isomer 1 (eq 1, Scheme 1).5a This method has
been widely adopted in the syntheses of natural products that
contain such a structural motif.5 More recently, a catalytic
Received: October 8, 2020
https://dx.doi.org/10.1021/acs.orglett.0c03366
© XXXX American Chemical Society
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A

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Scheme 1. Approaches for Enantioselective Syntheses of
1,2-anti- and 1,2-syn-2-Hydroxymethyl-3-ene-1-ols
Scheme 2. Stereoselective Syntheses of (E)- and (Z)-γ-
Borylmethyl Allylboronates 3 and 4
complex coordinates to one alkene unit of diene 7 to form Cu-
complex III, which undergoes 1,2-borocupration to give
allylcopper intermediate IV. Subsequent protonation of
allylcopper IV with MeOH proceeds via an SE2′ pathway to
give (E)-γ-borylmethyl allylboronate 3 with high (E)-
selectivity. On the other hand, IPr-ligated Cu-Bpin forms
complex V with diene 7. Then, a 1,4-borocupration occurs to
give (Z)-allylcopper species VI. Direct SE2 protonation of
allylcopper VI produces (Z)-γ-borylmethyl allylboronate 4
selectively. Experimental evidence to support the formation of
(Z)-allylcopper VI and the SE2 protonation pathway was
obtained from the stoichiometric reaction of the preformed
IPrCuCl complex, B2pin2, and NaOtBu with diene 7 and
subsequent protonation with MeOH. The coupling constant of
two olefinic protons of intermediate VI is 10.6 Hz, which is
consistent with a (Z)-alkene geometry. Protonation of (Z)-
allylcopper VI with MeOH gave allylboronate 4 (Supporting
Information).
After obtaining reagents 3 and 4, aldehyde allylation studies
with (E)-reagent 3 were conducted first. As shown in Scheme
3, a broad scope of aldehydes participated in reactions with 3
to give anti-products 8 in good yields with excellent
diastereoselectivities after in situ protection of the secondary
alcohol group as a TES-ether. Aromatic aldehydes with an
electron-donating or electron-withdrawing group at the para-
position reacted with 3 to afford anti-adducts 8a−c in 81−85%
yields. Reactions with aromatic aldehydes substituted with
chlorine at the para-, meta-, or ortho-position proceeded
smoothly to give products 8d−f in 71−85% yields. Similar
results were obtained from reactions with α,β-unsaturated
aldehydes, and anti-adducts 8g,h were obtained in 82−87%
yields. Aldehydes that contain a heterocycle are suitable
substrates for the allylation, and products 8i−l were isolated in
85−98% yields. Several representative aliphatic aldehydes also
reacted with 3 to deliver anti-products 8m−o in 71−88%
yields.
oxidation of the Bpin group in 5 and 6 will produce
enantioenriched and monoprotected 1,2-anti- and 1,2-syn-2-
hydroxymethyl-3-ene-1-ols (I and II, Scheme 1). Moreover,
the Bpin group in intermediates 5 and 6 should be amenable to
a variety of transformations in addition to oxidation.14,15 With
our continuing interests in carbonyl allylation chemistry,16 we
report herein enantioselective aldehyde addition with (E)- or
(Z)-γ-borylmethyl allylboronate, 3 or 4, to provide 1,2-anti- or
1,2-syn adducts in good yields with high enantioselectivities.
The method was successfully applied to the synthesis of natural
product morinol D.
We began our studies by developing suitable methods for
stereoselective syntheses of (E)- and (Z)-γ-borylmethyl
allylboronate reagents 3 and 4.17 After initial experimentations,
a Cu-catalyzed diene protoboration approach was identified for
stereoselective syntheses of 3 and 4.18 We discovered that, in
the presence of a bidentate phosphine ligand Xantphos, the
Cu(OMe)2-catalyzed protoboration of 1,3-dienylboronate 7
gave (E)-γ-borylmethyl allylboronate 3 in a 75% yield with a
>30:1 (E)-selectivity (Scheme 2a). The (Z)-isomer 4 was also
synthesized with high (Z)-selectivity from 1,3-dienylboronate
7 simply by replacing Xantphos with a monodentate NHC
ligand. (Z)-γ-Borylmethyl allylboronate 4 was obtained in a
73% yield with a >30:1 (Z)-selectivity (Scheme 2b). The
rationale for (E)- or (Z)-selective protoboration is shown in
Scheme 2. We propose that the Xantphos-ligated Cu-Bpin
Next, we explored the scope of aldehydes that participated in
the syn-(borylmethyl)allylation reaction with (Z)-allylboronate
B
https://dx.doi.org/10.1021/acs.orglett.0c03366
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a
Scheme 3. Aldehyde Scope for anti-
(Borylmethyl)allylation
Scheme 4. Aldehyde Scope for syn-(Borylmethyl)allylation
a
a
Reaction conditions are as follows: allylboronate 4 (0.13 mmol, 1.3
equiv), aldehyde (0.1 mmol, 1.0 equiv), and toluene (0.3 mL) at rt,
then TESCl (1.5 equiv), imidazole (2.0 equiv), and DMF (0.2 mL) at
rt. Yields of isolated products are listed.
a
Reaction conditions are as follows: allylboronate 3 (0.13 mmol, 1.3
equiv), aldehyde (0.1 mmol, 1.0 equiv), and toluene (0.3 mL) at rt,
then TESCl (1.5 equiv), imidazole (2.0 equiv), and DMF (0.2 mL) at
rt. Yields of isolated products are listed.
4, and the results are summarized in Scheme 4. The allylation
tolerates a variety of aldehydes, including aromatic aldehydes
with different substitution patterns, α,β-unsaturated aldehydes,
aldehydes with a heterocycle, and aliphatic aldehydes. In all
cases, 1,2-syn adducts 9 were formed as a single diastereomer
in 69−92% yields.
91% ee, as summarized in Scheme 6. Reactions with 2-
thiophene carboxaldehyde and hydrocinnamaldehyde gave
products 6h,i, respectively, in 79−86% yields with moderate
enantioselectivities (70−74% ee). The anti- and syn-relative
configurations of 5 and 6 were assigned by the coupling
constant analyses of the corresponding acetonides (Supporting
Information).
To access enantioenriched 1,2-anti or 1,2-syn products, 5 or
6, asymmetric allylations with boronate 3 or 4 were conducted
in the presence of chiral phosphoric acid (R)-A. As shown in
Scheme 5, the reaction between benzaldehyde and (E)-
allylboronate 3 with 5 mol % acid (R)-A as the catalyst
occurred at −45 °C in toluene. After in situ protection of the
secondary alcohol group, anti-adduct 5a was obtained in 84%
yield with 99% ee. Using this protocol, a collection of
aldehydes, ortho-substituted aromatic aldehydes and aliphatic
aldehydes in particular, reacted with allylboronate 3 to give
anti-products 5b−i in 71−98% yields with 90−99% ee.19
Asymmetric aldehyde allylation with (Z)-reagent 4 turned
out to be more challenging. We noticed that (Z)-allylboronate
4 was much less reactive than (E)-isomer 3 toward aldehyde
addition. Additionally, the enantioselectivities of syn-adducts 6
are generally lower than the optical purities of anti-adducts 5,
presumably owing to the uncatalyzed background reactions.
Nevertheless, reactions of 4 with representative aldehydes
occurred to give syn-adducts 6a−g in 62−88% yields with 81−
To demonstrate the synthetic utility of this method, the total
synthesis of natural product morinol D was conducted.20 As
shown in Scheme 7, the asymmetric allylation of veratralde-
hyde (10) with (E)-allylboronate 3, followed by oxidative
workup, gave anti-hydroxymethyl-1,3-diol 11 in a 73% yield
with 94% ee. Protection of the alcohol groups in 11 with excess
TIPSCl only occurred at the primary alcohol group. The
secondary OH group of 11 was converted to a TES ether by
adding TESCl to the reaction mixture, affording product 12 in
an 85% yield. The hydroboration−oxidation of 12 with 9-BBN
produced alcohol 13 in a 97% yield, which underwent Dess-
Marin oxidation to give 14 in an 86% yield. Aldehyde 14 was
transformed to vinyl boronate 16 in a 65% yield and >30:1
(E)-selectivity by using the olefination protocol developed by
the Morken group.21 The Pd-catalyzed Suzuki coupling of 16
with 4-iodoanisole (17), followed by deprotection of the silyl
ethers with TBAF, gave morinol D (18) in a 65% yield over
two steps.
C
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Scheme 5. Enantioselective anti-(Borylmethyl)allylation of
Aldehydes with (E)-Allylboronate 3
Scheme 7. Enantioselective Synthesis of Morinol D
a b c
, ,
a
Reaction conditions are as follows: allylboronate 3 (0.1 mmol, 1.0
equiv), aldehyde (0.2 mmol, 2.0 equiv), phosphoric acid (R)-A (5
mol %), 4 Å molecular sieves (25 mg), and toluene (0.3 mL) at − 45
°C, then TESCl (1.5 equiv), imidazole (2.0 equiv), and DMF (0.2
b
mL) at rt. Enantioselectivities were determined by HPLC analysis
using a chiral stationary phase. Yields of isolated products are listed.
c
Scheme 6. Enantioselective syn-(Borylmethyl)allylation of
a bc
, ,
Aldehydes with (Z)-Allylboronate 4
In summary, we developed a chiral phosphoric acid-
catalyzed enantioselective anti- and syn-(borylmethyl)allylation
of aldehydes with (E)- and (Z)-γ-borylmethyl allylboronate
reagents 3 and 4, respectively. Reagents 3 and 4 were
synthesized via a Cu-catalyzed stereoselective protoboration of
1,3-dienylboronate 7 with either a bidentate phosphine ligand
or a monodentate NHC ligand. In the presence of a catalytic
amount of chiral phosphoric acid (R)-A, asymmetric aldehyde
allylation with (E)-reagent 3 gave anti-adducts 5 in good yields
with excellent enantioselectivities. Allylation reactions with
(Z)-reagent 4 also proceeded to deliver syn-adducts 6 in good
yields and enantioselectivities. The synthetic utility of the
method was demonstrated by the total synthesis of morinol D.
ASSOCIATED CONTENT
■
sı
* Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.orglett.0c03366.
1H and 13C NMR spectra for all new compounds (PDF)
a
Reaction conditions are as follows: allylboronate 4 (0.1 mmol, 1.0
equiv), aldehyde (0.2 mmol, 2.0 equiv), phosphoric acid (R)-A (5
mol %), 4 Å molecular sieves (25 mg), and toluene (0.3 mL) at − 45
°C, then TESCl (1.5 equiv), imidazole (2.0 equiv), and DMF (0.2
AUTHOR INFORMATION
■
b
Corresponding Author
mL) at rt. Enantioselectivities were determined by HPLC analysis
c
using a chiral stationary phase. Yields of isolated products are listed.
Ming Chen − Department of Chemistry and Biochemistry,
Auburn University, Auburn, Alabama 36849, United States;
orcid.org/0000-0002-9841-8274; Email: mzc0102@
auburn.edu
d
The reaction was conducted with 10 mol % acid (R)-A.
D
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Author
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Letter
́
(i) Lopez-Martínez, J. L.; Torres-García, I.; Rodríguez-García, I.;
́
Munoz-Dorado, M.; Alvarez-Corral, M. J. Org. Chem. 2019, 84, 806.
̃
Jiaming Liu − Department of Chemistry and Biochemistry,
Auburn University, Auburn, Alabama 36849, United States
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Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.orglett.0c03366
Notes
The authors declare no competing financial interest.
ACKNOWLEDGMENTS
Financial support provided by Auburn University is gratefully
acknowledged.
■
(6) (a) Cui, J.; Ohtsuki, A.; Watanabe, T.; Kumagai, N.; Shibasaki,
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