Kinetic Resolution of 2-N-Acylamido Tertiary Allylic Alcohols: Asymmetric Synthesis of Oxazolines

Article abstract of DOI:10.1002/adsc.202001051

A series of cyclohexyl-fused SPINOL-derived phosphoric acids (Cy-SPA) have been developed to catalyze the kinetic resolution of 2-N-acylamido tertiary allylic alcohols, providing access to chiral oxazolines bearing C-2 alkyl substituents with high enantioselectivities (with s-factors up to 153). Gram-scale reaction with 1 mol% catalyst loading and transformations of the chiral products demonstrates the value of these methods. (Figure presented.).

Full text of DOI:10.1002/adsc.202001051

Title: Kinetic Resolution of 2-N-Acylamido Tertiary Allylic Alcohols:
Asymmetric Synthesis of Oxazolines
Authors: Yongkai Pan, Qianwen Jiang, Subramani Rajkumar, Chaofan
Zhu, Jinglei Xie, Shaoze Yu, Yunrong Chen, Yu-Peng He, and
Xiaoyu Yang
This manuscript has been accepted after peer review and appears as an
Accepted Article online prior to editing, proofing, and formal publication
of the final Version of Record (VoR). This work is currently citable by
using the Digital Object Identifier (DOI) given below. The VoR will be
published online in Early View as soon as possible and may be different
to this Accepted Article as a result of editing. Readers should obtain
the VoR from the journal website shown below when it is published
to ensure accuracy of information. The authors are responsible for the
content of this Accepted Article.
To be cited as: Adv. Synth. Catal. 10.1002/adsc.202001051
Link to VoR: https://doi.org/10.1002/adsc.202001051

10.1002/adsc.202001051
Advanced Synthesis & Catalysis
Very Important Publication
COMMUNICATION
DOI: 10.1002/adsc.201((will be filled in by the editorial staff))
Kinetic Resolution of 2-N-Acylamido Tertiary Allylic Alcohols:
Asymmetric Synthesis of Oxazolines
Yongkai Panab, Qianwen Jianga, Subramani Rajkumara, Chaofan Zhua, Jinglei Xiea,
Shaoze Yua, Yunrong Chena, Yu-Peng He*b and Xiaoyu Yang*a
a
School of Physical Science and Technology, ShanghaiTech University, Shanghai 201210, China.
E-mail: yangxy1@shanghaitech.edu.cn
Key Laboratory of Petrochemical Catalytic Science and Technology, Liaoning Shihua University, Dandong Lu West 1,
b
Fushun 113001, China
E-mail: yupeng.he@lnpu.edu.cn
Received: ((will be filled in by the editorial staff))
Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/adsc.201######.((Please
delete if not appropriate))
benzoylation by Maruoka group[8], albeit with
Abstract. A series of cyclohexyl-fused SPINOL-derived
phosphoric acids (Cy-SPA) have been developed to relatively limited scope (Figure 1, a). On the other
catalyze the kinetic resolution of 2-N-acylamido tertiary
allylic alcohols, providing access to chiral oxazolines
bearing C-2 alkyl substituents with high enantioselectivities
(with s-factors up to 153). Gram-scale reaction with 1
mol% catalyst loading and transformations of the chiral
products demonstrates the value of these methods.
hand, the asymmetric intramolecular-type cyclization
is another powerful method for kinetic resolution of
tertiary alcohols, which can produce chiral
heterocycles bearing quaternary stereocenters
simultaneously. List group developed ingenious
kinetic resolution of tertiary alcohols via asymmetric
acetalizations[9]. Our group realized the kinetic
resolution of tertiary 2-alkoxycarboxamido allylic
alcohols[10] and 2-amido benzyl alcohols[11] enabled
by chiral phosphoric acid catalyzed intramolecular
cyclizations, generating chiral oxazolones and 4H-
3,1-benzoxazines (Figure 1, b).
Keywords: Asymmetric catalysis; Organocatalysis; Kinetic
resolution; Alcohols; Oxazolines; Novel spirocyclic
phosphoric acids
Chiral tertiary alcohols and their derivatives are
ubiquitous among a variety of bioactive natural
products and pharmaceuticals, however, their
efficient asymmetric catalytic synthesis remains a
significant challenge. The most straightforward
strategy, namely asymmetric additions of carbon-
centered nucleophiles to ketones[1], faces the
challenges of less reactivity and decreased
enantioface differentiation of ketone substrates and
the vulnerability of tertiary alcohol products under
harsh conditions. Kinetic resolution (KR) is one of
the most reliable and practical method to produce
enantioenriched
products[2],
and
numerous
asymmetric catalytic methods have been developed
for kinetic resolution of secondary alcohols, both
through enzymatic and non-enzymatic catalysis.
Analogously, the kinetic resolution of tertiary
alcohols is also much more challenging due to the
demand for spatial differentiation between three R
groups[3]. Nonetheless, several elegant methods for
kinetic resolution of tertiary alcohols via asymmetric
hydroxy-protection reactions have been developed,
including the asymmetric acylation by Miller group[4],
Zhao group[5] and Smith group[6], asymmetric
silylation by Oestreich group[7] and asymmetric
1
This article is protected by copyright. All rights reserved.

10.1002/adsc.202001051
Advanced Synthesis & Catalysis
Figure 1. Asymmetric catalytic synthesis of oxazolines.
We initiated our kinetic resolution study by
choosing 2-N-Piv substituted tertiary allylic alcohol
3a as model substrate. Treatment of racemic 3a with
Cy-SPA catalyst A1 (1 mol%) and activated 5 Å
molecular sieves (MS) at room temperature for 5
hours provided the oxazoline 2a with 83% ee and
recovered 3a with 41% ee, giving a selectivity factor
of 8.4[23] (Table 1, entry 1). Subsequently, the
synthesized Cy-SPA catalysts were screened in this
reaction (entries 2-7). Encouragingly, the 3,5-
bis(trifluoromethyl)phenyl substituted catalysts A7
provided the best kinetic resolution performances,
giving s-factor of 98, and clean reaction system as
well (entry 7). Switching the chiral scaffold of A7 to
SPINOL-type (CPA A8) halved the s-factor to 49
(entry 8), while switching the chiral scaffold to
BINOL-type (CPA A9) only provided the s-factor of
4.1 (entry 9). The sterically bulky CPA catalyst A10
was also investigated in this reaction, however, which
generated significant amount of byproduct in this
reaction, albeit still giving the recovered SM and
product with high enantioselectivities (entry 10).
Next, a range of solvents were examined in this
reaction, which indicated toluene still as the optimal
solvent (entries 11-14). Further decreasing the
Since the pioneer work of Akiyama and Terada on
using BINOL-derived chiral phosphoric acid (CPA)
catalysts[12] in asymmetric catalysis, last 15 years
have witnessed the tremendous development in the
field of CPA catalysis[13]. Alongside with the ortho-
substitutions of CPA catalysts, the chiral scaffolds
also played important roles in controlling the
enantioselectivities of these reactions. Thus, a variety
of chiral diol scaffolds have been utilized for
construction of CPA catalysts[14], and among which
the SPINOL-derived phosphoric acid (SPA)
catalyst[15] exhibited excellent performances in a
series of asymmetric reactions (Figure 1, c)[16]
.
However, the traditional synthetic route to chiral SPA
still suffered the tedious synthetic steps and
requirements of resolution using stoichiometric
amount of chiral reagents[17]. Consequently, the
development of highly efficient asymmetric catalytic
synthesis of novel SPA[18] is still highly demanding.
With our continuous interest on kinetic resolution of
tertiary alcohols and novel asymmetric reactions of
amido allylic alcohols[19], herein we describe the
kinetic resolution of 2-N-acylamido tertiary allylic
alcohols via intramolecular dehydrative condensation
enabled by novel cyclohexyl-fused SPINOL-derived
phosphoric acids (Cy-SPA), generating chiral
oxazolines bearing C-2 alkyl groups, which is also a
type of challenging oxazoline products to be accessed
via the known asymmetric catalytic approaches[20]
(Figure 1, d).
o
reaction temperature to 10 C provided the optimal
kinetic resolution conditions, under which an
improved s-factor of 126 was obtained (entry 15).
Table 1. Optimization of reaction conditions.
Recently, Ding and co-workers reported a highly
efficient method for asymmetric catalytic synthesis of
chiral
cyclohexyl-fused
SPINOLs
via
enantioselective hydrogenations[21]
,
which we
envisioned would be an idea starting material for
asymmetric synthesis of novel SPAs[22]. With this
idea in mind, we started our study by Suzuki coupling
of the known cyclohexyl-fused SPINOL derivative 1
(99% ee) with MeB(OH)2, which was followed by
deprotection of the O-Me groups and ortho-
iodination to provide the di-iodinated product 2 with
high efficiency (86% for 3 steps, Scheme 1). With
this key intermediate 2 in hand, a range of aryl
boronic acids were then coupled under Suzuki
coupling conditions to give the corresponding diols,
which were converted to Cy-SPAs A1-7 via
phosphoration and subsequent hydrolysis.
b
time eesb
eep
Cc
entry cat solvents
sd
(h)
5
(%)
41
90
26
83
99
55
94
-95
-38
-94
73
30
63
94
99
(%) (%)
1
2
3
4
5
A1
A2
A3
A4
A5
A6
A7
A8
A9
Tol
Tol
Tol
Tol
Tol
Tol
Tol
Tol
Tol
83
86
86
84
68
86
93
-86
-48
-91
82
93
93
90
92
37
51
26
48
58
40
50
52
44
51
47
24
40
51
8.4
42
8.6
49
30
18
98
49
4.1
81
22
37
53
67
1
1
0.5
0.5
1
6
7e
8e
9e
1
1
7
3
10f A10
Tol
11e
12e
13e
14e
A7
A7
A7
A7
DCM
CHCl3
CCl4
Et2O
Tol
1
1
1
8
15e,g A7
5
52 126
Scheme 1. Synthesis of chiral cyclohexyl-fused SPINOL-
aReactions were performed with 3a (0.1 mmol), CPA
(0.001mol, 1 mol%) in solvents (1 mL) with 5 Å MS (40
mg) at room temperature for designated time. Ee values
derived
phosphoric
acids.
dppf
SPhos
=
1,1'-
2-
Bis(diphenylphosphino)ferrocene,
=
b
Dicyclohexylphosphino-2',6'-dimethoxybiphenyl.
2
This article is protected by copyright. All rights reserved.

10.1002/adsc.202001051
Advanced Synthesis & Catalysis
were determined by HPLC analysis on a chiral stationary
meta- and sterically demanding ortho-substituted
phenyl groups (3l-3p). The naphthyl group (3q) and
the heteroaryl group (3r) were also well tolerated at
this position. Next, the scope for alkylacyl groups at
the 2-N-position of allylic alcohol substrates was
examined. The bulky 1-adamantanyl group was
amenable substituent, giving s-factor of 65 (3s). The
less bulky alkyl substituted 2-oxazolines were
relatively challenging products for asymmetric
catalytic synthesis according to previous reports[20m,
20n]. Encouragingly, kinetic resolution of a secondary
alkylacyl substituted 2-amido allylic alcohols under
the standard conditions proceeded smoothly to give
the product 4t with 90% ee and recovered SM with
85% ee. Furthermore, the primary alkylacyl
substituted 2-amido allylic alcohols could be
kinetically resolved with high s-factors as well, albeit
c
1
phase. Conversion were determined by H NMR analysis
d
of the crude reaction mixture. s = ln[(1-C)(1-ees)]/ln[(1-
C)(1+ees)]. eConversions were determined by
ees/(ees+eep). fWith 5 mol% catalyst. gAt 10 oC.
C =
With the optimal kinetic resolution conditions in
hand, we first examined the scope of various
substituents at the 1-position of 2-N-Piv substituted
tertiary allylic alcohols (Table 2). A series of para-
and meta-substituted phenyl groups were well
tolerated at the 1-position of allylic alcohols,
regardless of the electronic nature of substituents (3b-
3f). The absolute configurations of the products were
assigned by analogy to (S)-3a, whose absolute
structure was unambiguously determined by X-Ray
crystallography[24]. Next, a variety of alkyl groups at
the 1-position of allylic alcohols were also examined
in this reaction, which were also amenable with the
optimal condition (3g-3j), including the benzyl group
(3i) and allyl group (3j), albeit with a bit diminished
s-factors. Finally, an 1,1-dialkyl substituted 2-amido
allylic alcohol substrate 3k was also investigated
under the standard kinetic resolution conditions,
which was also well resolved, giving s-factor of 62
(3k).
the
SPINOL-derived
2,4,6-triisopropylphenyl
substituted CPA (R)-A10 (5 mol%) was used instead
(3u-3w).
Table 3. Scope for kinetic resolution of 2-amido allylic
alcohols regarding to variants at the 3- and 2-N positions.
Table 2. Scope for kinetic resolution of 2-amido tertiary
allylic alcohols regarding to variants at the 1-position.
aReactions were performed with the same conditions as
b
o
c
indicated in Table 2. At -20 C. With (R)-A10 (0.01
mmol, 5 mol%). dAt 0 oC.
To demonstrate the practicability of this method,
kinetic resolution of 4.0 mmol of racemic 3a (1.29 g)
under the standard condition was performed, which
provided the (S)-3a in 49% yield with 91% ee and 4a
in 49% yield with 94% ee, with an s-factor of 103
(Scheme 2, a). Kinetic resolution of the racemic 2-
amido secondary allylic alcohol 5a was also studied,
which provided the (S)-5a in 40% yield with 98% ee;
however, oxazoline 6a was isolated as the major
product, with the chiral center eliminated via double
bond isomerization (Scheme 2, b). To showcase the
applicability of these methods, the derivatizations of
the chiral products were also conducted. Treatment of
aReactions were performed with 3 (0.2 mmol), (S)-A7
(0.002 mol, 1 mol%) in toluene (2 mL) with 5 Å MS (80
o
mg) at 10 C. Yields were isolated yields. Ee values were
determined by HPLC analysis on a chiral stationary phase.
s = ln[(1-C)(1-ees)]/ln[(1-C)(1+ees)]. C = ees/(ees+eep).
bWith (S)-A7 (0.01 mmol, 5 mol%). cAt -20 oC.
The scope for variants at the 3-position of racemic
tertiary allylic alcohols were also studied (Table 3). A
series of substituted phenyl groups were compatible
with the optimal conditions, including various para-,
3
This article is protected by copyright. All rights reserved.

10.1002/adsc.202001051
Advanced Synthesis & Catalysis
of (S)-catA7 (1.6 mg, 1 mol%) in toluene (0.1 mL) was
added slowly. After achieving suitable conversion as
monitored by chiral HPLC analysis, the reaction mixture
was quenched by adding Et3N (10 uL) and resulting
mixtures was purified by column chromatography to give
the recovered (S)-3 and product 4.
the (S)-3a with racemic phosphoric acid catalysts
PA1 (1 mol%) readily provided the oxazoline (S)-4a
in 98% yield with retained enantiomeric excess,
providing important insight on the reaction
mechanism, in which the hydroxy group played as the
nucleophile and the amide moiety as the electrophile
under the promotion of CPA catalyst (Scheme 2, c)[11]
Hydrogenation (1 atm) of (R)-4a using Raney Ni as
catalyst gave the oxazoline product 7a in 73% yield,
with >25:1 dr, which underwent the hydrolysis in the
presence of TFA to afford the β-amino tertiary
alcohol 8a in 80% yield with 94% ee (Scheme 2, d).
Additionally, direct hydrolysis of oxazoline (R)-4a in
.
Acknowledgements
We gratefully acknowledge NSFC (Grant No. 21702138,
21901162) for financial support. We thank the support from
Analytical Instrumentation Center (# SPST-AIC10112914), SPST,
ShanghaiTech University and Dr. Na Yu for X-ray
crystallographic analysis.
the presence of TFA and H2O readily afforded the α-
hydroxy ketone 9a, without diminishment of
enantioselectivity.
References
[1] a) P. G. Cozzi, R. Hilgraf, N. Zimmermann, Eur. J.
Org. Chem. 2007, 2007, 5969-5994; b) O. Riant, J.
Hannedouche, Org. Biomol. Chem. 2007, 5, 873-888;
c) M. Shibasaki, M. Kanai, Chem. Rev. 2008, 108,
2853-2873; d) Y.-L. Liu, X.-T. Lin, Adv. Synth. Catal.
2019, 361, 876-918.
[2] a) D. E. J. E. Robinson, S. D. Bull, Tetrahedron:
Asymmetry 2003, 14, 1407-1446; b) E. Vedejs, M.
Jure, Angew. Chem. Int. Ed. 2005, 44, 3974-4001; c)
C. E. Müller, P. R. Schreiner, Angew. Chem. Int. Ed.
2011, 50, 6012-6042; d) H. Pellissier, Adv. Synth.
Catal. 2011, 353, 1613-1666; e) R. Gurubrahamam,
Y.-S. Cheng, W.-Y. Huang, K. Chen, ChemCatChem
2016, 8, 86-96; f) Z. Wang, D. Pan, T. Li, Z. Jin,
Chem. Asian J. 2018, 13, 2149-2163; g) H. Yang,
W.-H. Zheng, Tetrahedron Lett. 2018, 59, 583-591.
[3] a) S.-y. Tosaki, K. Hara, V. Gnanadesikan, H.
Morimoto, S. Harada, M. Sugita, N. Yamagiwa, S.
Matsunaga, M. Shibasaki, J. Am. Chem. Soc. 2006,
128, 11776-11777; b) R. Shintani, K. Takatsu, T.
Hayashi, Org. Lett. 2008, 10, 1191-1193; c) W.
Zhang, S. Ma, Chem. Commun. 2018, 54, 6064-6067.
[4] E. R. Jarvo, C. A. Evans, G. T. Copeland, S. J. Miller,
J. Org. Chem. 2001, 66, 5522-5527.
Scheme 2. Gram-scale reaction, kinetic resolution of 2-
amido secondary allylic alcohol and derivatizations of
chiral products.
[5] S. Lu, S. B. Poh, W.-Y. Siau, Y. Zhao, Angew. Chem.
Int. Ed. 2013, 52, 1731-1734.
[6] a) M. D. Greenhalgh, S. M. Smith, D. M. Walden, J.
E. Taylor, Z. Brice, E. R. T. Robinson, C. Fallan, D.
B. Cordes, A. M. Z. Slawin, H. C. Richardson, M. A.
Grove, P. H.-Y. Cheong, A. D. Smith, Angew. Chem.
Int. Ed. 2018, 57, 3200-3206; b) S. Qu, S. Smith, V.
Laina, R. M. Neyyappadath, M. Greenhalgh, A. D.
Smith, Angew. Chem. Int. Ed. 2020, DOI:
10.1002/anie.202004354.
[7] J. Seliger, X. Dong, M. Oestreich, Angew. Chem. Int.
Ed. 2019, 58, 1970-1974.
[8] M. Pawliczek, T. Hashimoto, K. Maruoka, Chem. Sci.
2018, 9, 1231-1235.
[9] a) I. Čorić, S. Müller, B. List, J. Am. Chem. Soc. 2010,
132, 17370-17373; b) J. H. Kim, I. Čorić, C. Palumbo,
B. List, J. Am. Chem. Soc. 2015, 137, 1778-1781.
[10] S. Rajkumar, S. He, X. Yang, Angew. Chem. Int. Ed.
2019, 58, 10315-10319.
In conclusion, we have disclosed an efficient protocol
for kinetic resolution of 2-N-acylamido tertiary allylic
alcohols enabled by a type of novel spirocyclic
phosphoric acids (Cy-SPA) catalysts, generating 2-
alkyl-substituted oxazolines with high stereoselectivities.
A series of variants were well tolerated at the 1- and 3-
positions of the 2-amido allylic alcohols, as well as
various alkylacyl groups at the 2-N-position, which gave
s-factors up to 153. Gram-scale reaction with low
catalyst loading (1 mol%) and facile transformations of
the chiral products demonstrate the synthetic potential
of these methods.
Experimental Section
[11] S. Rajkumar, M. Tang, X. Yang, Angew. Chem. Int.
Ed. 2020, 59, 2333-2337.
To a 4 mL vial containing a stirring bar was added racemic
3 (0.2 mmol) and activated 5 Å MS (80 mg). After adding
o
toluene (2 mL) via syringe and cooling to 10 C, a solution
4
This article is protected by copyright. All rights reserved.

10.1002/adsc.202001051
Advanced Synthesis & Catalysis
[12]a) T. Akiyama, J. Itoh, K. Yokota, K. Fuchibe, Angew.
Chem. Int. Ed. 2004, 43, 1566-1568; b) D. Uraguchi,
M. Terada, J. Am. Chem. Soc. 2004, 126, 5356-5357.
[13] a) T. Akiyama, Chem. Rev. 2007, 107, 5744-5758; b)
M. Terada, Synthesis 2010, 2010, 1929-1982; c) D.
Parmar, E. Sugiono, S. Raja, M. Rueping, Chem. Rev.
2014, 114, 9047-9153; d) T. Akiyama, K. Mori, Chem.
Rev. 2015, 115, 9277-9306; e) X. Li, Q. Song, Chin.
Chem. Lett. 2018 29, 1181-1192; f) A. Rahman, X.
Lin, Org. Biomol. Chem. 2018, 16, 4753-4777.
[14] a) T. Akiyama, Y. Saitoh, H. Morita, K. Fuchibe, Adv.
Synth. Catal. 2005, 347, 1523-1526; b) G. B.
Rowland, H. Zhang, E. B. Rowland, S.
Chennamadhavuni, Y. Wang, J. C. Antilla, J. Am.
Chem. Soc. 2005, 127, 15696-15697; c) J. Stemper, K.
Isaac, V. Duret, P. Retailleau, A. Voituriez, J.-F.
Betzer, A. Marinetti, Chem. Commun. 2013, 49,
6084-6086; d) K. Isaac, J. Stemper, V. Servajean, P.
Retailleau, J. Pastor, G. Frison, K. Kaupmees, I. Leito,
J.-F. Betzer, A. Marinetti, J. Org. Chem. 2014, 79,
9639-9646; e) Y. Wang, W. Liu, W. Ren, Y. Shi, Org.
Lett. 2015, 17, 4976-4979; f) E. Xie, S. Huang, X. Lin,
Org. Lett. 2019, 21, 3682-3686; g) K. Mori, K. Ehara,
K. Kurihara, T. Akiyama, J. Am. Chem. Soc. 2011,
133, 6166-6169.
[20] a) S. D. Pastor, A. Togni, J. Am. Chem. Soc. 1989,
111, 2333-2334; b) D. A. Evans, J. M. Janey, N.
Magomedov, J. S. Tedrow, Angew. Chem. Int. Ed.
2001, 40, 1884-1888; c) H. Y. Kim, K. Oh, Org. Lett.
2011, 13, 1306-1309; d) F. Sladojevich, A. Trabocchi,
A. Guarna, D. J. Dixon, J. Am. Chem. Soc. 2011, 133,
1710-1713; e) R. de la Campa, I. Ortín, D. J. Dixon,
Angew. Chem. Int. Ed. 2015, 54, 4895-4898; f) P.
Martínez-Pardo, G. Blay, M. C. Muñoz, J. R. Pedro,
A. Sanz-Marco, C. Vila, Chem. Commun. 2018, 54,
2862-2865; g) P. Martínez-Pardo, G. Blay, C. Vila, A.
Sanz-Marco, M. C. Muñoz, J. R. Pedro, J. Org. Chem.
2019, 84, 314-325; h) A. Jaganathan, A. Garzan, D. C.
Whitehead, R. J. Staples, B. Borhan, Angew. Chem.
Int. Ed. 2011, 50, 2593-2596; i) V. Rauniyar, A. D.
Lackner, G. L. Hamilton, F. D. Toste, Science 2011,
334, 1681; j) Y. Tsuda, M. Kuriyama, O. Onomura,
Chem. Eur. J. 2012, 18, 2481-2483; k) Y. Kawato, A.
Kubota, H. Ono, H. Egami, Y. Hamashima, Org. Lett.
2015, 17, 1244-1247; l) Y. Nagao, T. Hisanaga, H.
Egami, Y. Kawato, Y. Hamashima, Chem. Eur. J.
2017, 23, 16758-16762; m) H. Luo, Z. Yang, W. Lin,
Y. Zheng, S. Ma, Chem. Sci. 2018, 9, 1964-1969; n)
R. Kuwano, N. Kameyama, R. Ikeda, J. Am. Chem.
Soc. 2011, 133, 7312-7315.
[15] a) F. Xu, D. Huang, C. Han, W. Shen, X. Lin, Y.
Wang, J. Org. Chem. 2010, 75, 8677-8680; b) C.-H.
Xing, Y.-X. Liao, J. Ng, Q.-S. Hu, J. Org. Chem.
2011, 76, 4125-4131.
[21] a) Z. Zheng, Y. Cao, Q. Chong, Z. Han, J. Ding, C.
Luo, Z. Wang, D. Zhu, Q.-L. Zhou, K. Ding, J. Am.
Chem. Soc. 2018, 140, 10374-10381; b) M. Wu, Z.
Han, K. Li, J. e. Wu, K. Ding, Y. Lu, J. Am. Chem.
Soc. 2019, 141, 16362-16373; c) Z. Zheng, Y. Cao, D.
Zhu, Z. Wang, K. Ding, Chem. Eur. J. 2019, 25,
9491-9497.
[22] W.-Y. Ding, P. Yu, Q.-J. An, K. L. Bay, S.-H. Xiang,
S. Li, Y. Chen, K. N. Houk, B. Tan, Chem 2020 DOI:
10.1016/j.chempr.2020.06.001..
[16] a) B. Xu, S.-F. Zhu, X.-L. Xie, J.-J. Shen, Q.-L. Zhou,
Angew. Chem. Int. Ed. 2011, 50, 11483-11486; b) Z.
Chen, B. Wang, Z. Wang, G. Zhu, J. Sun, Angew.
Chem. Int. Ed. 2013, 52, 2027-2031; c) A. Martínez,
M. J. Webber, S. Müller, B. List, Angew. Chem. Int.
Ed. 2013, 52, 9486-9490; d) Z.-L. Tao, A. Adili, H.-C.
Shen, Z.-Y. Han, L.-Z. Gong, Angew. Chem. Int. Ed.
2016, 55, 4322-4326; e) S.-G. Wang, Z.-L. Xia, R.-Q.
Xu, X.-J. Liu, C. Zheng, S.-L. You, Angew. Chem. Int.
Ed. 2017, 56, 7440-7443.
[23] H. B. Kagan, J. C. Fiaud, Topics in Stereochemistry,
Vol. 18 (Eds.: E. L. Eliel, S. H. Wilen), Wiley, New
York, 1988, pp. 249 – 330.
[24] CCDC-2018771
contains
the
supplementary
[17] J.-H. Zhang, J. Liao, X. Cui, K.-B. Yu, J. Zhu, J.-G.
Deng, S.-F. Zhu, L.-X. Wang, Q.-L. Zhou, L. W.
Chung, T. Ye, Tetrahedron: Asymmetry 2002, 13,
1363-1366.
crystallographic data for this paper. These data can be
obtained free of charge from The Cambridge
Crystallographic
Data
Centre
via
www.ccdc.cam.ac.uk/data_request/cif.
[18]a) S. Li, J.-W. Zhang, X.-L. Li, D.-J. Cheng, B. Tan, J.
Am. Chem. Soc. 2016, 138, 16561-16566; b) L. Wang,
J. Zhong, X. Lin, Angew. Chem. Int. Ed. 2019, 58,
15824-15828.
[19] a) S. He, H. Gu, Y.-P. He, X. Yang, Org. Lett. 2020,
22, 5633–5639; b) S. Rajkumar, J. Wang, X. Yang,
Synlett 2019, 30, 869-874; c) S. Rajkumar, J. Wang, S.
Zheng, D. Wang, X. Ye, X. Li, Q. Peng, X. Yang,
Angew. Chem. Int. Ed. 2018, 57, 13489-13494.
5
This article is protected by copyright. All rights reserved.

10.1002/adsc.202001051
Advanced Synthesis & Catalysis
COMMUNICATION
Kinetic Resolution of 2-N-Acylamido Tertiary
Allylic Alcohols: Asymmetric Synthesis of
Oxazolines
Adv. Synth. Catal. Year, Volume, Page – Page
Yongkai Panab, Qianwen Jianga, Subramani
Rajkumara, Chaofan Zhua, Jinglei Xiea, Shaoze
Yua, Yunrong Chena, Yu-Peng He*b and Xiaoyu
Yang*a
6
This article is protected by copyright. All rights reserved.