Direct Construction of NOBINs via Domino Arylation and Sigmatropic Rearrangement Reactions

Chinese Journal

of Chemistry

CJC

中国化学 - An International Journal

Accepted Article

Title: Direct Construction of NOBINs via Domino Arylation and Sigmatropic

Rearrangement Reactions

Authors: Ji-Wei Zhang, Liang-Wen Qi, Shaoyu Li,* Shao-Hua Xiang, and Bin Tan*

This manuscript has been accepted and appears as an Accepted Article online.

This work may now be cited as: Chin. J. Chem. 2020, 38, 10.1002/cjoc.202000358.

The final Version of Record (VoR) of it with formal page numbers will soon be

published online in Early View: http://dx.doi.org/10.1002/cjoc.202000358.

ISSN 1001-604X • CN 31-1547/O6

mc.manuscriptcentral.com/cjoc

www.cjc.wiley-vch.de

Chinese Journal

of Chemistry

Biaryls, Sigmatropic rearrangement, Diarylhaloniums, Metal-free,

Arylation

Report

CJC

中

国化学 - An International Journal

Direct Construction of NOBINs via Domino Arylation and Sigmatropic

Rearrangement Reactions

Ji-Wei Zhang,^a,bLiang-Wen Qi,^bShaoyu Li,*^,b,cShao-Hua Xiang,^b,cand Bin Tan*^,b

^aSchool of Chemistry and Chemical Engineering, Harbin Institute of Technology, Harbin 150001, China

^bShenzhen Grubbs Institute and Department of Chemistry, Southern University of Science and Technology, Shenzhen, 518055, China

^cAcademy for Advanced Interdisciplinary Studies, Southern University of Science and Technology, Shenzhen, 518055, China

Cite this paper: Chin. J. Chem. 2019, 37, XXX—XXX. DOI: 10.1002/cjoc.201900XXX

Summary of main observation and conclusion

Privileged NOBIN frameworks were constructed through a novel domino arylation of

naphthylhydroxylamines with diarylhalonium salts and sigmatropic rearrangement in a transition metal-free fashion. This protocol bears broad substrate

generality and proceeds under mild reaction conditions, affording diversified NOBINs in high efficiency with absolute regiocontrol during the

rearrangement process. Optically active product was accessible by chiral NHC-catalyzed kinetic resolution in one pot or diastereoselective

[3,3]-rearrangement guided by a removable chiral auxiliary. Remarkably, diarylchloronium and diarylbrominium salts have been employed as arylation

reagents for the first time in assembling such representative biaryl frameworks.

metal-catalyzed oxidative cross-coupling of 2-naphthol and

2-naphthylamine. This popular strategy was pioneered by

Kočovský and coworkers with copper and amine complex as the

catalyst (Figure 2a).^[3d]Following this work, Ding^[3f]and Carriera^[3g]

disclosed improved solutions to enhance synthetic efficiency;

poor applicability in large-scale preparation, harsh reaction

Background and Originality Content

2-Amino-2’-hydroxy-1,1’-binaphthyl

(NOBIN)

and

its

derivatives find widespread applications as pivotal chiral catalysts

and ligands in enantioselective transformations,^[1]encompassing

various

subdomains

including

metal

catalysis,^[1e-h]

organocatalysis,^[1i-j]photocatalysis^[1k]or even heterogeneous

catalysis^[1l]. The cumulating successes present these atropisomers

as a class of privileged non-C₂-symmetric binaphthyl structures

(Figure 1). They also constitute the core structural unit in a series

of functional materials.^[2]As resolution of racemic NOBINs has

been now well-developed, it becomes the method of choice to

acquire enantioenriched NOBIN reliably. It follows that deriving

more streamlined access toward NOBIN or its analogues is the

cornerstone for advancing different disciplines that draw utility

from this class of biaryls.^[3]

a)

chemical

transformation

or

NH₂

OH

[Cu] [Fe]

NH₂

OH

NH₂

OH

+

b)

NO₂

X

+

MgBr

EWG

O

[3,3]-

rearrangement

OH

H

NH₂

OH

=

or

Cl Br

X

N

EWG

+

N

O

X

LG

EWG electron-withdrawing

OH

H

example

NO

Mes

N

Cl

Et

Br

O

=

group

N

P

Ru

O

OH

PPh₂

OH

c)

N

OiPr

NHC

tBu

Ar

Imine

ligand

Ar

Hybrid phosphorus ligand

F₃C

ligand

Ar

[3,3]-

rearrangement

Y

X

Ar

R

NH₂

OH

F

N

O

Arylation

F

=

X

Br, Cl

S

I,

HN

O

NH₂

OH

N

H

P

Ar

NOBINs

Diversified NOBINs

N

H

O

NH

OH

and

nucleophiles

Transition metal-free

Versatile

reagents

arylation

Complete regioselectivity

Ar

F₃C

NOBIN

Diaminodioxaphosphonium

Organo-photocatalyst

Figure 2 Representative strategies for the synthesis of NOBIN and

NOBIN-type biaryls.

Figure 1 Selected chiral catalysts and ligands bearing NOBIN backbone.

While routine conversions from other binaphthyl structures

are highly enabling,^[3a-c]a more expedite and economical access

resides in forming the aryl-aryl axis directly by transition

conditions as well as inseparable homo-coupling byproducts

nonetheless conspire to its considerably high production cost

(sold at $150/g, Macklin). Accordingly, a robust and cost-effective

This article has been accepted for publication and undergone full peer review but has not been

through the copyediting, typesetting, pagination and proofreading process which may lead to

differences between this version and the Version of Record. Please cite this article as doi:

10.1002/cjoc.202000358

Zhang et al.

Report

preparation method, preferably in transition metal-free setting,

appears highly appealing. In this context, [3,3]-sigmatropic

rearrangement frequently brought to bear on Ar-Ar bond

formation proved to be an attractive option.^[4]Kürti and

co-workers elegantly adopted this strategy to assemble biaryl

amino alcohols from N,O-disubstituted hydroxylamine

intermediates generated in situ by the reaction between aryl

Grignard reagent and nitrobenzene or nucleophilic substitution

reaction of N-phenylhydroxylamine to electron-deficient arene

with a leaving group (Figure 2b).^[4b,4h]These seminal works set the

stage for our conjecture to assemble NOBIN derivatives from two

aryl units without transition metal catalyst. Further, a protocol

that takes in more general aryl partners is particularly enticing.

This addresses the substrate restriction in previous chemistry

where special functionalities are required to confer reactivity in

forming the rearrangement precursors.

(entries 12, 15-16). Noticeably, regiospecific aryl group transfer

was operational with the use of unsymmetrical diaryliodonium

salt carrying a 2-methoxybenzene as “dummy ligand” (entry 13).

Table 1 Optimization of the reaction conditions.^a

X

I

Ar

base

OH

+

Cbz

N

r.t.

NHCbz

solvent,

1a

OH

:

=

2a

2b

2c

X

BF₄

OTf

PF₆

3a

Entry

Solvent

X

Base

Yield (%)^b

1

2

DCM

toluene

THF

BF₄

OTf

PF₆

Na₂CO₃

K₂CO₃

70

38

47

74

78

< 5

76

75

38

63

95

93

60

91

88

3

Diaryliodonium salts^[5]as a class of bench-stable, nontoxic and

readily available aryl cation equivalents are stalwart reaction

partners in various successful transition metal-free arylation

reactions, including those that forge biaryls and heterobiaryls.^[6]

We therefore contemplate to exploit this reactivity of

dinaphthyliodonium salt into our envisioned [3,3]-sigmatropic

rearrangement strategy, thereby unleash the shackles on

substrate requirement. To this end, several challenges will be

encountered: 1) selection of suitable nucleophilic naphthyl

reagent; 2) efficient formation of the transient intermediate

before rearrangement; 3) regioselectivity control in

[3,3]-sigmatropic rearrangement; 4) mild reaction conditions to

accommodate wide-scope functional groups. In accordance with

our continuous efforts on biaryl syntheses,^[7]we herein present

our recent findings in diversified synthesis of NOBINs via an

arylation and [3,3]-sigmatropic rearrangement sequence under

mild conditions in the absence of transition metal catalyst. A

group of diarylhalonium salts were effectively utilized and both

4

MeCN

MeOH

TFE

5

6

7

MeOH

8

Cs₂CO₃

Na₃PO₄

NaOtBu

iPr₂NEt

Na₂CO₃

9

10

11

12^c

13^c,d

14^c,e

15^c

16^c

DCM/TFE (5/1)

^aUnless otherwise specified, all reactions were performed with 1a (0.10

mmol), diaryliodonium salt 2a (Ar = 2-naphthyl, 0.10 mmol) and base (0.12

b

mmol) in solvent (2.0 mL) at room temperature for 24 h. Yield was

determined by ¹H-NMR analysis of the crude reaction mixture using

N-/O-naphthylhydroxylamines

were

verified

competent

nucleophiles for this transformation (Figure 2c).^[8]To the best of

our knowledge, the employment of diarylchloronium and

diarylbrominium salts as arylation reagent in this type of reactions

was unexampled.

c

1,3,5-trimethoxybenzene as internal standard. 2a (0.12 mmol) and

d

e

Na₂CO₃(0.13 mmol) were used.

Ar

=

2-methoxyphenyl.

Ar =

2,4,6-trimethylphenyl. TFE = Trifluoroethanol (CF₃CH₂OH).

With the optimal reaction conditions in hand, the substrate

scope of this transformation was then explored with respect to

N-naphthylhydroxylamines. All examined substrates underwent

complete conversion within 24 h in generally good efficiency with

recorded yield up to 92% (Table 2). Our study commenced by

modulating the N-protecting groups of 1 where Cbz group was

found to be best suited, as inferred from the highest product yield

(3a). With regards to substituent effects, NOBIN structures that

bear electron-withdrawing (3h-3k) or electron-donating moieties

(3f, 3l and 3m) were consistently formed in excellent yields. As

such, current protocol was minimally influenced by electronic

fluctuation of aromatic ring on hydroxylamine partner due to

varied substituents introduced at differing positions. This included

a pyrrole moiety which indiscriminately afforded 3l in good yield.

Results and Discussion

As

a starting point, N-naphthylhydroxylamine 1a and

diaryliodonium salt 2a were probed for the hypothesized

arylation/[3,3]-rearrangement cascade using Na₂CO₃as base in

dichloromethane (DCM) at room temperature (r.t.). Encouragingly,

the desired product 3a was obtained in 70% yield (Table 1, entry

1), along with several by-products. When evaluating different

solvents (entries 2-6), methanol fortuitously afforded the best

result with yield approximated to 80%. Various inorganic bases

appeared to offer better outcomes than organic amine (entries

7-11).

A

binary solvent mixture comprising DCM and

trifluoroethanol (TFE) was conspicuously beneficial; when coupled

with fine-tuned stoichiometry of reactants and base, these

conditions culminated in completely regioselective formation of

3a in 95% yield. Application of diaryliodonium salts bearing

different counter-anions invariably provided good conversions

Table 2. Substrate scope of N-naphthylhydroxylamines.^a.b

www.cjc.wiley-vch.de

Chin. J. Chem. 2019, 37, XXX－XXX

Running title

Chin. J. Chem.

^aUnless otherwise specified, all reactions were performed with 1 (0.20

mmol), diaryliodonium salt 2 (Ar = 2-methoxyphenyl, 0.24 mmol) and

Na₂CO₃(0.26 mmol) in DCM/TFE (5/1, 4.0 mL) at room temperature for 24

h. ^bIsolated yield. ^cAr = 2,4,6-trimethylphenyl. ^dAr = 6-F-2-naphthyl.

BF₄

R²

Na₂CO₃

DCM/TFE

I

OH

NHR¹

R¹

+

N

r.t., 24 h

(5/1),

R²

OH

1

2a

3

OH

NHCbz

OH

NHCO₂Me

OH

NHBoc

OH

NHCOPh

OH

NHTs

To further expand the synthetic flexibility of this methodology,

we became interested with the prospect of employing

O-naphthylhydroxylamines. Almost no expected product was

obtained when 4a was tested; instead, O-arylated 5a was

identified. Upon optimizing the stoichiometry of 2a, choices of

base and solvent, the following conditions were concluded as

optimal: 4a and 2a in a molar ratio of 1.0:2.2 were treated with

Cs₂CO₃(1.5 equiv) in toluene at room temperature for 12 h to

generate 5a in exellent yield (see the Supporting Information for

details). Same set of conditions was applied to investigate the

generality of this re-optimized system. As shown in Table 4,

O-naphthylhydroxylamines 4 undertook coupling reaction readily,

leading to products 5a-5i in high yields (up to 95%) which carried

various protecting and functional groups. Notably, the reaction

used an unsymmetrical salt (2g) which exhibited two-fold

selection toward single regioisomer of 5j. Replacement of

2-naphthyl with 9-phenanthryl (2n) on diaryliodonium salt

resulted in limited influence in the reaction efficiency (5l and 5m).

3e 51%

3a 92%

3b 90%

3c 71%

3d 64%

,

yield

OH

NHCbz

MeO

Ph

F

Br

Cl

3f 84%

,

3g 88%

,

yield

3j 90%

,

yield

3i

3h 83%

,

, 88%

yield

OH

NHBoc MeO

OH

NH

OH

NH

OH

NH

NHCbz

Ph

Br

Cbz

MeO₂C

N

3k 93%

,

3l 70%

,

3m

3n

3o

, 85%

, 92%

yield

^aAll reactions were performed with 1 (0.20 mmol), 2a (0.24 mmol) and

Na₂CO₃(0.26 mmol) in DCM/TFE (5/1, 4.0 mL) at r.t. for 24 h. ^bIsolated

yields.

We next explored the generality of the reaction to

accommodate varying diaryliodonium salt partners. A broad

range of diaryliodonium salts containing different aryl

substituents reacted smoothly with N-naphthylhydroxylamines to

produce NOBIN derivatives 3 in up to 94% yield, which consisted

of halides, methyl ester, phenyl, methoxy (Table 3, 3p-3v).

Similarly, the position and electronic nature of these substituents

imposed negligible effect on the transformation efficiency;

extended fused ring system was no exception (3w). When

Table 4. Substrate generality of O-arylhydroxylamines^a

R¹

BF₄

6

Cs₂CO₃

I

O

R¹

+

NHR

toluene r.t., 12 h

7

O

2a

5

4

different combinations of N-naphthylhydroxylamines

1 and

diaryliodonium salts 2 possessing varied substitutions were

treated under standard conditions, multi-substituted NOBINs

3x-3ai were forged with commendable efficiencies (78−91% yield).

It should be emphasized that preservation of bromide handle in

these molecular outputs signifies access to more diversified

NOBIN scaffolds through well-established cross-coupling

reactions.

Entry

R

R¹

5

yield (%)^b

1

2

3^c

4

5

6

7

8

9

Cbz

H

5a

5b

5c

5d

5e

5f

95

91

84

90

95

93

91

92

86

CO₂Et

POPh₂

Ts

H

Cbz

6-MeO

6-Me

6-CO₂Me

7-MeO

7-Br

Table 3. Substrate scope of diaryliodonium salts.^a,b

Cbz

5g

5h

5i

R²

BF₄

R¹

Na₂CO₃

I

OH

Cbz

+

Ar

Cbz

R²

N

NHCbz

DCM/TFE

r.t., 24 h

(5/1),

F

R¹

OH

1

2

3

Cbz

MeO

Ph

Br

MeO

₂C

Ph

OMe

OH

NHCbz

OH

NHCbz

OH

NH

BF₄

Cs₂CO₃

NHCbz

I

O

Cbz

+

NHCbz

toluene, r.t., 12 h

O

Ph

c

3p 61%

3q 85%

3r 86%

3s 83%

3t

, 90%

,

yield

4a

2g

5j

70%

,

yield

Ph

Br

F

OH

Ph

F

OH

Br

OH

BF₄

Cs₂CO₃

O

+

I

NHCbz

toluene, r.t., 12 h

Br

F

4a

2i

5k

,

90%

yield

3x 88%

,

3y 86%

,

3u 86%

3v 94%

,

3w 91%

,

yield

,

yield

F

MeO₂C

OH

NHCbz

OH

NH

Br

OH

NH

OH

NH

R

BF₄

NHCbz

Cbz

I

R

Cs₂CO₃

r.t., 12 h

O

+

F

MeO₂C

MeO

MeO₂C

d

3z 78%

,

3aa 81%

,

3ab

3ac

, 86%

3ad

, 82%

NH

Cbz

NHCbz

, 85%

yield

toluene,

O

4

2n

Ph

OH

Br

OH

Ph

Br

OH

Br

OH

=

R

H

5l 88%

, ,

yield

OMe 5m 90%

NHCbz Br

NHCbz

NHCbz MeO

NHCbz

MeO

NHCbz

,

yield

3ae 84%

,

3af 82%

,

3ag 81%

,

3ah 91%

,

3ai 89%

,

yield

^aUnless otherwise specified, all reactions were performed with 4 (0.20

Chin. J. Chem. 2019, 37, XXX－XXX

www.cjc.wiley-vch.de

Zhang et al.

Report

mmol), diaryliodonium salt 2 (0.44 mmol) and Cs₂CO₃(0.30 mmol) in

toluene (4.0 mL) at room temperature for 12 h. ^bIsolated yields were

provided. ^cReaction was performed for four days.

(3a, 82% yield) was secured with THF as reaction medium at room

temperature (Figure 4a). Herewith, three types of diarylhalonium

salts have been verified as suitable arylation reagents in current

NOBIN construction protocol. Moreover, 3a was isolated in 25%

yield when the reaction was performed with 1:1 stoichiometry of

4a and 2r. In the excess of 2r (2.2 equiv), 5a in turn was produced

in 93% yield (Figure 4b).

On the basis of previous reports concerning iodine(III)

reagents^[5e,9]and our understandings on the construction of

biaryls, a plausible reaction process was rationalized as follows

(using 1 as model): The preceding O-arylation step adopts a ligand

coupling pathway where intermediacy of arynes and radicals

could be ruled out (see Supporting Information for details). In the

absence of transition metal, an anion exchange giving rise to

T-shaped intermediate^[9b-d]or tetra-coordinated intermediate

could be operative,^[10]in accordance with the widely accepted

mechanisms. A formal [1,3]-rearrangement follows to provide key

arylated intermediate and expels the iodoarene in a regiospecific

fashion. [3,3]-rearrangement of the in situ-generated transient

N,O-binaphthylhydroxylamine ensues only at the α-position of

naphthalene ring to afford NOBIN derivatives 3 with exclusive

regioselectivity. This implies the [3,3]-rearrangement is an overall

energetically favorable event which comprises N-O bond cleavage,

new Ar-Ar bond formation and rearomatization. In addition,

a)

Cbz

N

mmol) OH

=

1a

(0.10

Ar

Na₂CO THF

,

OH

3

MeO

NHCbz

=

r.t., 48 h

X

Cl 81%

82%

81%

yield

Ar

BAr_f4

mol)

=

X

Br

82%

3a

2

(0.11

=

BAr_f4

tetrakis(3,5-bis(trifluoromethyl)phenyl)borate

b)

O

Cbz

N

H

mmol)

4a

(0.10

Conditions

r.t., 12 h

OH

O

+

NHCbz

OMe

BAr_f4

Cl

2r

3a

5a

Conditions A:

Conditions B:

,

2r

(2.2

DIPEA, DCM

Cs₂CO₃toluene

,

equiv)

yield;

equiv)

(1.0

3a

,

5a

93%

,

25%

36%

,

yield

compound

3 can be further arylated quantitatively to 5.

N-arylhydroxylamine substrates participated controllably and

selectively towards 3 or 5. O-arylhydroxylamines conversely

presented 5 as the sole products. A reactivity order of 1

(N-arylhydroxylamine) > 3 (naphthol) > 4 (O-arylhydroxylamine)

towards arylation with iodonium salts could thus be inferred from

these data. In short, the observed C_(Ar)–C_(Ar)formation should

follow an uninterrupted course of anion exchange,

[1,3]-rearrangement, [3,3]-sigmatropic rearrangement and

rearomatization (Figure 3).

Figure 4. Investigations with diarylchloronium and diarylbrominium salts

as aryl cation equivalents.

A

gram-scale reaction delivered 3a in analogous yield,

implying that this protocol should be well suited for large-scale

chemical production. Three analogously efficient methods to

remove Cbz protecting group were demonstrated feasible, which

could be adopted at will according to compatibility of functional

groups present (Figure 5a). We further approached the synthesis

of enantiomerically enriched NOBIN by a diastereoselective

[3,3]-rearrangement. With commercially available and

inexpensive (1R, 2S, 5R)-(-)-menthol as chiral auxiliary,

N-(-)-menthoxycarbonylhydroxylamine 1p was facilely prepared

and treated with 2a under standard conditions. Diastereoselective

arylation-rearrangement occurred with high efficiencies.

Diastereomerically pure 3aj and 3ak were subsequently

hydrolyzed to afford atropisomeric pair of NOBIN 6a (Figure 5b).

Y

2

base

OH

H

O

H

Ar

+

N

X

N

1

2

OH

3

5

base

anion exchange

[3,3]-

rearrangement

activity

Arylation

‡

Ar-OH

OR

‡

3

X

Ar

X

Ar

O

N

O

N

or

O

N

4

1

ArO-NH

OH

ArN(R)-

(R)

transient intermediate

T-shaped intermediate

4-coordinated intermediate

Figure 3. Plausible reaction pathway for the synthesis of NOBINs via

arylation and [3,3]-sigmatropic rearrangement sequence.

Utilization of diarylchloronium and diarylbrominium salts, on

the other hand, was rarely considered although they have been

long known. The highly electron-deficient nature arising from the

large ionization potential and excellent leaving-group ability

should invite their use as aryl cation equivalent. For a more

comprehensive picture, we synthesized diarylchloronium and

diarylbrominium as per modified literature method^[11]to

investigate the compatibility and/or superiority of these

diarylhalonium salts in constructing NOBIN derivatives. Although

the developed conditions were found inapplicable, a solvent

screen aided to restore good reaction efficiency. The best result

www.cjc.wiley-vch.de

Chin. J. Chem. 2019, 37, XXX－XXX

Running title

Chin. J. Chem.

Experimental

a)

KOH

EtOH, reflux

yield

(aq.),

95%

mmol)

1a

2a

(3.0

+

mmol)

Na₂CO

Pd/C, H₂, MeOH/CHCl₃

90%

₃(3.5

OH

I. General procedures for synthesis of NOBIN derivatives 3.

Compound 1 (0.20 mmol), 2 (0.24 mmol) and Na₂CO₃(0.26 mmol)

were added to a bottle with a stirring bar. Pre-mixed solvent

DCM/CF₃CH₂OH (5/1, 4mL) was added and the reaction mixture

was stirred for 24 h at room temperature till 1 was completely

consumed (monitored by TLC). After evaporated the solvent, the

residue was purified by flash chromatography eluted with DCM to

afford the corresponding product 3.

NHCbz

NH₂

yield

DCM/CF CH OH 1)

(5/

3

2

(3.3

con.

HCl, AcOH, reflux

90%

yield

3a

Rac 6a

95%)

O

g,

(1.19

(

)-

b)

O

2a

+

N

O

N

H

Standard

conditions

N

O

OH

1p

OH

3aj 41%

3ak

, 50%

,

yield

Benzyl (2'-hydroxy-[1,1'-binaphthalen]-2-yl)carbamate (3a):

white solid, 77.1 mg, 92% yield. H NMR (400 MHz, CDCl₃) δ 8.56

KOH

EtOH, reflux

I

(aq.),

Ar

1

BF₄

=

2a

Ar

(d, J = 9.2 Hz, 1H), 8.08 (d, J = 9.2 Hz, 1H), 7.99 (d, J = 9.2 Hz, 1H),

7.93 (t, J = 8.4 Hz, 2H), 7.45 (t, J = 7.2 Hz, 1H), 7.41-7.37 (m, 2H),

7.34-7.26 (m, 7H), 7.13 (d, J = 8.4 Hz, 1H), 7.03 (d, J = 8.4 Hz, 1H),

6.51 (s, 1H), 5.09 (s, 2H), 5.03 (s, 1H). ¹³C NMR (100 MHz, CDCl₃) δ

153.6, 152.0, 135.9, 135.7, 133.2, 132.9, 131.3, 130.8, 130.4,

129.4, 128.6, 128.5, 128.4, 128.3, 128.3, 127.5, 127.4, 125.3,

125.1, 124.1, 124.0, 119.7, 117.9, 116.6, 112.7, 67.1. HRMS (ESI)

calcd for [M+H] C₂₈H₂₂NO₃, m/z: 420.1594, found: 420.1594.

Methyl (2'-hydroxy-[1,1'-binaphthalen]-2-yl)carbamate (3b):

white solid, 61.7 mg, 90% yield. ¹H NMR (400 MHz, Acetone-d₆) δ

8.48 (d, J = 9.2 Hz, 1H), 8.43 (s, 1H), 8.03 (d, J = 9.2 Hz, 1H), 8.00 (d,

J = 9.2 Hz, 1H), 7.92 (t, J = 7.2 Hz, 2H), 7.43 (d, J = 8.8 Hz, 1H), 7.37

(t, J = 7.6 Hz, 1H), 7.30 (t, J = 7.6 Hz, 1H), 7.24-7.19 (m, 2H), 7.08

(d, J = 8.4Hz, 1H), 6.96-6.93 (m, 2H), 3.51 (s, 3H). ¹³C NMR (100

MHz, Acetone-d₆) δ 153.9, 153.5, 135.4, 133.9, 133.4, 130.8,

130.7, 129.2, 128.8, 128.4, 128.1, 127.0, 126.5, 125.4, 124.5,

124.0, 123.4, 119.9, 119.7, 118.7, 113.4, 51.5. HRMS (ESI) calcd

for [M+H] C₂₂H₁₈NO₃, m/z: 344.1281, found: 344.1280.

tert-Butyl (2'-hydroxy-[1,1'-binaphthalen]-2-yl)carbamate (3c):

pale yellow solid, 54.8 mg, 71% yield. ¹H NMR (400 MHz, CDCl₃) δ

8.52 (d, J = 9.2 Hz, 1H), 8.06 (d, J = 8.8 Hz, 1H), 8.01 (d, J = 8.8 Hz,

1H), 7.94 (d, J = 3.6 Hz, 1H), 7.92 (d, J = 4.0 Hz, 1H), 7.45-7.38 (m,

3H), 7.32-7.27 (m, 2H), 7.09 (d, J = 8.8Hz, 1H), 7.05 (d, J = 8.4 Hz,

1H), 6.27 (s, 1H), 5.09 (s, 1H), 1.41 (s, 9H). ¹³C NMR (100 MHz,

CDCl₃) δ 153.2, 152.0, 136.4, 133.4, 133.0, 131.1, 130.7, 130.2,

129.4, 128.4, 128.3, 127.3, 127.2, 125.1, 125.0, 124.4, 123.9,

120.2, 118.0, 116.6, 113.1, 81.0, 28.2. HRMS (ESI) calcd for [M+H]

C₂₅H₂₄NO₃, m/z: 386.1751, found: 386.1746.

,

2-naphthyl

O

NH₂

OH

NH₂

OH

N

O

N

iPr

H

Cl

OBz

6a

Br

S

R

7

8

(

)-

(

)-

ee

95%

99%

95%

99%

yield,

c)

Cbz

N

O

7

8

mol%)

(10

1a

OH

DIPEA

equiv)

(0.58

OH

NHCbz

O

iBu

Cbz

+

NH

THF, r.t., 48 h

0 °C to r.t., 48 h

OMe

BAr_f4

Cl

2r

3a

)-

ee

91%

R

9a

)-

ee

56%

S

(

43%

32%

yield,

Figure 5. a) Gram-scale synthesis of 3a and the removal of protecting

group; b) Diastereoselective [3,3]-sigmatropic rearrangement; c) Chiral

NHC-catalyzed kinetic resolution.

The dearth of universal asymmetric approaches towards

enantiopure NOBINs^[12]often restricts the scope of applications. A

one-pot two-step synthesis that integrates kinetic resolution after

arylation-rearrangement is thus especially handy. Inspired by

NHC-catalyzed kinetic resolution of NOBINs by Zhao and

co-workers,^[13]this synthetic operation was undertaken using

diarylchloronium 2r and naphthylhydroxylamines 1a. Upon

completion of NOBIN formation, α-aryloxy aldehyde 8 and chiral

azolium salt 7 were administered. Pleasingly, the combination of

DIPEA and THF was well accommodated by both steps to arrive at

(S)-3a in 32% yield and 91% ee (Figure 5c).

N-(2'-hydroxy-[1,1'-binaphthalen]-2-yl)benzamide (3d): white

solid, 49.8 mg, 64% yield. ¹H NMR (400 MHz, DMSO-d₆) δ 9.94 (s,

1H), 8.74 (s, 1H), 8.35 (d, J = 8.8 Hz, 1H), 8.11 (d, J = 8.8 Hz, 1H),

8.03 (t, J = 8.8 Hz, 2H), 7.93 (d, J = 8.0 Hz, 1H), 7.50-7.45 (m, 3H),

7.36-7.32 (m, 5H), 7.29 (t, J = 7.2 Hz, 1H), 7.21 (t, J = 7.2 Hz, 1H),

7.15 (d, J = 8.0 Hz, 1H), 6.95 (d, J = 8.4 Hz, 1H). ¹³C NMR (100 MHz,

DMSO-d₆) δ 165.4, 153.7, 135.1, 135.0, 133.9, 133.1, 132.1, 131.5,

130.7, 128.9, 128.7, 128.6, 128.5, 128.4, 127.2, 127.1, 126.7,

126.2, 125.5, 125.1, 124.5, 123.4, 123.2, 118.9, 114.1. HRMS (ESI)

calcd for [M+H] C₂₇H₂₀NO₂, m/z: 390.1489, found: 390.1485.

N-(2'-hydroxy-[1,1'-binaphthalen]-2-yl)-4-methylbenzenesulfo

namide (3e): white solid, 44.8 mg, 51% yield. ¹H NMR (400 MHz,

CDCl₃) δ 8.01 (d, J = 9.2 Hz, 1H), 7.87 (t, J = 9.6 Hz, 2H), 7.77 (d, J =

8.0 Hz, 2H), 7.35 (d, J = 8.0 Hz, 2H), 7.30 (t, J = 7.2 Hz, 1H), 7.24 (t,

J = 7.2 Hz, 1H), 7.18 (d, J = 8.8 Hz, 1H), 7.02-6.97 (m, 1H),

7.16-7.12 (m, 3H), 6.92 (d, J = 8.4 Hz, 1H), 6.53 (d, J = 8.4 Hz, 1H),

6.37 (s, 1H), 4.47 (s, 1H), 2.24 (s, 3H). ¹³C NMR (100 MHz, CDCl₃) δ

Conclusions

In summary, we have described a transition metal-free

approach to generate NOBIN derivatives following facile O- or

N-arylation and highly regioselective [3,3]-sigmatropic

rearrangement sequence. From easily accessible diarylhalonium

salts and naphthylhydroxylamines, a broad scope was applicable

and N-capping group of the latter was removable with ease under

mild conditions. The N,O-dinaphthylhydroxylamine was virtually

not isolable, indicating

rearrangement. Enantiomerically pure products were procurable

with either one-pot NHC-catalyzed kinetic resolution or

a strong driving force for the

diastereoselective rearrangement. We also demonstrated

a

pioneering example where diarylchloronium and diarylbrominium

salts served as aryl transfer reagents in the construction of biaryls.

Studies are ongoing in our group to apply this domino strategy for

the construction of other binaphthyl skeletons.

Chin. J. Chem. 2019, 37, XXX－XXX

www.cjc.wiley-vch.de

Zhang et al.

Report

151.9, 144.1, 135.9, 134.7, 133.0, 133.0, 131.6, 131.2, 130.7,

129.7, 129.3, 128.5, 128.3, 127.6, 127.5, 127.2, 125.7, 125.3,

124.0, 123.7, 119.1, 118.2, 117.8, 111.9, 21.6. HRMS (ESI) calcd

for [M+H] C₂₇H₂₂NO₃S, m/z: 440.1315, found: 440.1319.

Benzyl

(m, 7H), 7.20-7.11 (m, 2H), 7.00 (d, J = 8.4 Hz, 1H), 5.07 (s, 2H). ¹³

C

NMR (100 MHz, Acetone-d₆) δ 160.0 (d, J = 241.7 Hz), 153.6, 153.5,

136.6, 135.0 (d, J = 2.5 Hz), 133.8, 131.5 (d, J = 9.1 Hz), 130.8,

130.4, 129.1, 128.4, 128.4, 128.3 (d, J = 9.8 Hz), 128.1 (d, J = 5.2

Hz), 128.0, 128.0, 127.1, 123.9, 123.4, 121.6, 121.1, 118.7, 116.3

(d, J = 25.1 Hz), 113.3, 110.5 (d, J = 20.5 Hz), 66.2. ¹⁹F NMR (375

(2'-hydroxy-6-methoxy-[1,1'-binaphthalen]-2-yl)carbamate (3f):

white solid, 75.4 mg, 84% yield. ¹H NMR (400 MHz, Acetone-d₆) δ

8.43 (d, J = 9.2 Hz, 1H), 8.42 (s, 1H), 7.99 (dd, J = 9.2, 6.4 Hz, 2H),

7.93 (d, J = 8.0 Hz, 1H), 7.45 (d, J = 8.8 Hz, 1H), 7.40 (d, J = 2.4 Hz,

1H), 7.34 (t, J = 7.6 Hz, 1H), 7.30-7.23 (m, 6H), 7.20 (s, 1H), 7.06 (d,

MHz, Acetone-d₆)

δ -118.5. HRMS (ESI) calcd for [M+H]

C₂₈H₂₁FNO₃, m/z: 438.1500, found: 438.1500.

Methyl

2-(((benzyloxy)carbonyl)amino)-2'-hydroxy-[1,1'-binaphthalene]-6

J = 8.8 Hz, 1H), 7.03 (d, J = 8.8 Hz, 1H), 6.96 (dd, J = 9.2, 2.8 Hz, 1H), -carboxylate (3k): pale yellow solid, 88.7 mg, 93% yield. ¹H NMR

5.06 (s, 2H), 3.90 (s, 3H). ¹³C NMR (100 MHz, Acetone-d₆) δ 157.1,

153.7, 153.4, 136.7, 133.9, 133.4, 132.2, 130.6, 129.1, 128.6,

128.4, 128.3, 127.9, 127.9, 127.6, 127.1, 126.9, 124.1, 123.3,

121.2, 121.0, 119.0, 118.7, 113.9, 106.3, 66.1, 55.8. HRMS (ESI)

calcd for [M+H] C₂₉H₂₄NO₄, m/z: 450.1700, found: 450.1704.

Benzyl

(400 MHz, Acetone-d₆) δ 8.69 (d, J = 2.0 Hz, 1H), 8.65 (d, J = 8.8 Hz,

1H), 8.23 (d, J = 9.2 Hz, 1H), 8.00 (d, J = 9.2 Hz, 1H), 7.99 (s, 1H),

7.91 (dd, J = 8.4, 1.2 Hz 1H), 7.81 (dd, J = 9.2, 1.6 Hz, 1H), 7.45 (d, J

= 8.8 Hz, 1H), 7.38 (s, 1H), 7.32 (d, J = 8.0 Hz, 1H), 7.28-7.22 (m,

6H), 7.19 (d, J = 9.2 Hz, 1H), 6.97 (d, J = 8.4 Hz, 1H), 5.06 (s, 2H),

3.89 (s, 3H). ¹³C NMR (100 MHz, Acetone-d₆) δ 166.5, 153.7, 153.4,

137.8, 136.4, 135.7, 133.8, 131.0, 131.0, 130.3, 129.7, 129.1,

128.5, 128.4, 128.0, 128.0, 127.1, 126.1, 125.8, 125.6, 123.8,

123.4, 120.6, 120.3, 118.7, 112.8, 66.4, 51.6. HRMS (ESI) calcd for

[M+H] C₃₀H₂₄NO₅, m/z: 478.1649, found: 478.1646.

(2'-hydroxy-6-phenyl-[1,1'-binaphthalen]-2-yl)carbamate

(3g):

pale yellow solid, 87.1 mg, 88% yield. ¹H NMR (400 MHz, CDCl₃) δ

8.62 (d, J = 8.8 Hz, 1H), 8.18-8.13 (m, 2H), 8.04 (d, J = 8.8, Hz, 1H),

7.98 (d, J = 8.0, Hz, 1H), 7.73 (d, J = 7.6 Hz, 2H), 7.61 (d, J = 8.8 Hz,

1H), 7.55-7.28 (m, 12H), 7.16 (d, J = 8.4 Hz, 1H), 6.67 (s, 1H), 5.76

(s, 1H), 5.10-5.01 (m, 2H). ¹³C NMR (100 MHz, CDCl₃) δ 153.7,

152.3, 140.7, 137.9, 135.9, 135.8, 133.3, 132.3, 131.3, 131.2,

130.5, 129.5, 129.0, 128.6, 128.5, 128.4, 128.3, 127.5, 127.5,

127.3, 127.0, 126.2, 125.9, 124.2, 124.1, 120.2, 118.2, 117.2,

tert-Butyl

(2'-hydroxy-6-(1H-pyrrol-1-yl)-[1,1'-binaphthalen]-2-yl)carbamate

(3l): white solid, 63.0 mg, 70% yield. ¹H NMR (400 MHz, CDCl₃) δ

8.55 (d, J = 9.2 Hz, 1H), 8.03 (t, J = 9.6 Hz, 2H), 7.96 (d, J = 8.0 Hz,

1H), 7.87 (d, J = 2.4 Hz, 1H), 7.44-7.41 (m, 2H), 7.38 (dd, J = 9.2,

112.8, 67.2. HRMS (ESI) calcd for [M+H] C₃₄H₂₆NO₃, m/z: 496.1907, 2.0 Hz, 1H), 7.33 (t, J = 8.0 Hz, 1H), 7.19-7.18 (m, 2H), 7.16 (d, J =

found: 496.1909.

9.6 Hz, 1H), 7.08 (d, J = 8.4 Hz, 1H), 6.41-6.40 (m, 2H), 6.30 (s, 1H),

5.23 (s, 1H), 1.43 (s, 9H). ¹³C NMR (100 MHz, CDCl₃) δ 153.1, 152.0,

137.6, 136.2, 133.3, 131.2, 131.1, 131.0, 129.8, 129.4, 128.4,

127.5, 126.9, 124.3, 124.0, 121.4, 121.3, 119.5, 118.0, 117.8,

Benzyl

(6-bromo-2'-hydroxy-[1,1'-binaphthalen]-2-yl)carbamate

(3h):

white solid, 82.5 mg, 83% yield. ¹H NMR (400 MHz, Acetone-d₆) δ

8.59 (d, J = 9.2 Hz, 1H), 8.58 (s, 1H), 8.20 (d, J = 2.0 Hz, 1H), 8.06 (d, 116.8, 112.8, 110.7, 81.2, 28.2. HRMS (ESI) calcd for [M+H]

J = 8.8 Hz, 1H), 8.01 (d, J = 8.8 Hz, 1H), 7.93 (d, J = 8.0 Hz, 1H), 7.45

(d, J = 8.8 Hz, 1H), 7.39 (dd, J = 9.2, 2.0 Hz, 1H), 7.34 (t, J = 7.6 Hz,

2H), 7.30-7.24 (m, 6H), 7.07 (d, J = 8.8 Hz, 1H), 7.00 (d, J = 8.4 Hz,

1H), 5.07 (s 2H). ¹³C NMR (100 MHz, Acetone-d₆) δ 153.6, 153.5,

136.5, 136.1, 133.8, 132.0, 131.9, 130.9, 130.0, 129.5, 129.2,

128.4, 128.4, 128.0, 128.0, 128.0, 127.7, 127.1, 123.8, 123.5,

C₂₉H₂₇N₂O₃, m/z: 451.2016, found: 451.2019.

Benzyl

(2'-hydroxy-7-methoxy-[1,1'-binaphthalen]-2-yl)carbamate (3m):

white solid, 82.6 mg, 92% yield. ¹H NMR (400 MHz, Acetone-d₆) δ

8.44 (s, 1H), 8.39 (d, J = 8.8 Hz, 1H), 8.00 (d, J = 8.8 Hz, 1H), 7.99 (d,

J = 8.8 Hz, 1H), 7.93 (d, J = 8.0 Hz, 1H), 7.90 (d, J = 9.2 Hz, 1H), 7.46

121.3, 120.7, 118.7, 118.0, 112.9, 66.3. HRMS (ESI) calcd for [M+H] (d, J = 8.8 Hz, 1H), 7.34 (d, J = 7.6 Hz, 1H), 7.30-7.25 (m, 6H), 7.19

C₂₈H₂₁BrNO₃, m/z: 498.0699, found: 498.0695.

Benzyl

(6-chloro-2'-hydroxy-[1,1'-binaphthalen]-2-yl)carbamate

(s, 1H), 7.11 (dd, J = 9.2, 2.8 Hz, 1H), 7.06 (d, J = 8.4 Hz, 1H), 6.51

(d, J = 2.8 Hz, 1H), 5.07 (s, 2H), 3.45 (s, 3H). ¹³C NMR (100 MHz,

Acetone-d₆) δ 158.4, 153.5, 153.4, 136.6, 136.0, 134.8, 133.7,

130.7, 129.7, 129.2, 128.6, 128.4, 128.4, 128.0, 127.9, 126.9,

126.3, 124.0, 123.4, 119.2, 118.7, 117.5, 116.5, 113.6, 104.6, 66.2,

54.3. HRMS (ESI) calcd for [M+H] C₂₉H₂₄NO₄, m/z: 450.1700, found:

450.1702.

(3i):

white solid, 79.7 mg, 88% yield. ¹H NMR (400 MHz, CDCl₃) δ 8.55

(d, J = 9.6 Hz, 1H), 7.99 (dd, J = 8.8, 2.4 Hz, 1H), 7.96-7.91 (m, 3H),

7.45-7.22 (m, 9H), 7.08 (dd, J = 9.2, 2.0 Hz, 1H), 7.00 (d, J = 8.4 Hz,

1H), 6.56 (s, 1H), 5.48 (s, 1H), 5.06 (d, J = 12.0 Hz, 1H), 5.01 (d, J =

12.0 Hz, 1H). ¹³C NMR (100 MHz, CDCl₃) δ 153.6, 152.1, 136.0,

135.6, 133.1, 131.5, 131.4, 131.4, 131.1, 129.4, 129.3, 128.6,

128.5, 128.4, 128.3, 128.1, 127.6, 127.0, 126.9, 124.1, 124.0,

120.9, 118.1, 117.4, 112.2, 67.3. HRMS (ESI) calcd for [M+H]

C₂₈H₂₁ClNO₃, m/z: 454.1204, found: 454.1200.

Benzyl

(2'-hydroxy-7-phenyl-[1,1'-binaphthalen]-2-yl)carbamate

(3n):

white solid, 91.1 mg, 92% yield. ¹H NMR (400 MHz, Acetone-d₆) δ

8.40 (d, J = 8.8 Hz, 1H), 8.07 (d, J = 8.8 Hz, 1H), 8.03 (d, J = 8.4 Hz,

1H), 7.98 (d, J = 9.2 Hz, 1H), 7.90 (d, J = 8.0 Hz, 1H), 7.74-7.72 (m,

1H), 7.69 (d, J = 8.4, 2.0 Hz, 1H), 7.38 (d, J = 8.8 Hz, 1H), 7.36-7.19

(m, 13H), 7.02 (s, 1H), 6.99 (d, J = 8.4 Hz, 1H), 5.03 (s, 2H). ¹³C

NMR (100 MHz, Acetone-d₆) δ 153.7, 153.6, 141.0, 139.0, 136.6,

Benzyl

(6-fluoro-2'-hydroxy-[1,1'-binaphthalen]-2-yl)carbamate

(3j):

white solid, 78.7 mg, 90% yield. ¹H NMR (400 MHz, Acetone-d₆) δ

8.56 (s, 1H), 8.55 (d, J = 9.2 Hz, 1H), 8.07 (d, J = 9.2 Hz, 1H), 8.01 (d, 135.9, 133.9, 133.7, 130.8, 130.1, 129.1, 128.9, 128.8, 128.6,

J = 8.8 Hz, 1H), 7.94 (dd, J = 8.4, 1.2 Hz, 1H), 7.70 (dd, J = 10.0, 2.4

Hz, 1H), 7.45 (d, J = 9.2 Hz, 1H), 7.34 (t, J = 8.0 Hz, 1H), 7.30-7.24

128.5, 128.4, 128.0, 128.0, 127.3, 127.1, 127.0, 124.2, 124.0,

123.4, 123.3, 120.9, 120.3, 118.7, 113.5, 66.3. HRMS (ESI) calcd

www.cjc.wiley-vch.de

Chin. J. Chem. 2019, 37, XXX－XXX

Running title

Chin. J. Chem.

for [M+H] C₃₄H₂₆NO₃, m/z: 496.1907, found: 496.1905.

Benzyl

(d, J = 243.0 Hz), 153.66, 151.6 (d, J = 2.0 Hz), 135.89, 135.73,

132.89, 130.91, 130.58, 130.4 (d, J = 5.0 Hz), 130.13, 130.1(d, J =

9.0 Hz), 128.67, 128.51, 128.4, 128.4, 127.58, 126.6 (d, J = 8.0 Hz),

125.43, 125.00, 119.88, 119.29, 117.5 (d, J = 25.0 Hz), 116.65,

(7-bromo-2'-hydroxy-[1,1'-binaphthalen]-2-yl)carbamate

(3o):

white solid, 84.5 mg, 85% yield. ¹H NMR (400 MHz, Acetone-d₆) δ

8.61 (s, 1H), 8.38 (d, J = 8.8 Hz, 1H), 7.88 (d, J = 9.2 Hz, 1H), 7.81 (d, 113.16, 111.8 (d, J = 21.0 Hz), 67.29. ¹⁹F NMR (375 MHz, DMSO-d₆)

J = 8.4 Hz, 1H), 7.72 (t, J = 8.0 Hz, 2H), 7.31 (d, J = 8.8 Hz, 1H), 7.26

(d, J = 8.4 Hz, 1H), 7.14-7.03 (m, 9H), 6.80 (d, J = 8.4 Hz, 1H), 4.86

(s, 2H). ¹³C NMR (100 MHz, acetone-d₆) δ 153.7, 153.5, 136.6,

136.5, 134.7, 133.7, 131.0, 130.3, 129.3, 129.1, 128.8, 128.5,

128.4, 128.0, 128.0, 127.7, 127.3, 127.2, 123.7, 123.5, 120.6,

120.5, 119.8, 118.7, 112.7, 66.4. HRMS (ESI) calcd for [M+H]

C₂₈H₂₁BrNO₃, m/z: 498.0699, found: 498.0696.

δ -118.0. HRMS (ESI) calcd for [M+H] C₂₈H₂₁FNO₃, m/z: 438.1500,

found: 438.1502.

Methyl

2'-(((benzyloxy)carbonyl)amino)-2-hydroxy-[1,1'-binaphthalene]-6

1

-carboxylate (3t): white solid, 85.9 mg, 90% yield. H NMR (400

MHz, CDCl₃) δ 8.65 (d, J = 2.0 Hz, 1H), 8.51 (d, J = 9.2 Hz, 1H), 8.07

(dd, J = 8.8, 4.4 Hz, 2H), 7.93 (d, J = 8.0 Hz, 1H), 7.84 (dd, J = 8.8,

2.0 Hz, 1H), 7.42-7.47 (m, 2H), 7.35-7.29 (m, 4H), 7.27-7.24 (m,

2H), 7.09 (d, J = 8.4 Hz, 1H), 7.05 (d, J = 8.8 Hz, 1H), 6.47 (s, 1H),

5.58 (s, 1H), 5.05 (s, 2H), 3.95 (s, 3H). ¹³C NMR (100 MHz, CDCl₃) δ

167.2, 154.2, 153.6, 135.9, 135.7, 135.6, 132.8, 132.7, 131.6,

130.9, 130.6, 128.6, 128.4, 128.4, 128.4, 128.3, 127.5, 126.9,

125.6, 125.4, 124.8, 124.3, 119.9, 118.9, 116.3, 113.1, 67.2, 52.2.

HRMS (ESI) calcd for [M+H] C₃₀H₂₄NO₅, m/z: 478.1649, found:

Benzyl

(2'-hydroxy-6'-methoxy-[1,1'-binaphthalen]-2-yl)carbamate (3p):

pale yellow solid, 54.8 mg, 61% yield. ¹H NMR (400 MHz, CDCl₃) δ

8.55 (d, J = 8.8 Hz, 1H), 8.06 (d, J = 9.2 Hz, 1H), 7.93 (d, J = 8.4 Hz,

1H), 7.88 (d, J = 8.8 Hz, 1H), 7.45 (t, J = 7.4 Hz, 1H), 7.37-7.27 (m,

7H), 7.24 (d, J = 2.4Hz, 1H), 7.14 (d, J = 8.4 Hz, 1H), 6.98-6.92 (m,

2H), 6.52 (s, 1H), 5.09 (s, 2H), 4.94 (s, 1H), 3.93 (s, 3H). ¹³C NMR

(100 MHz, CDCl₃) δ 156.4, 153.6, 150.3, 135.8, 135.8, 132.9, 130.8, 478.1644.

130.4, 130.3, 129.9, 128.6, 128.4, 128.3, 128.3, 127.4, 125.7,

125.2, 125.1, 119.8, 119.7, 119.6, 118.4, 116.9, 113.0, 106.9, 67.1,

55.4. HRMS (ESI) calcd for [M+H] C₂₉H₂₄NO₄, m/z: 450.1700, found: white solid, 85.1 mg, 86% yield. H NMR (400 MHz, CDCl₃) δ 8.57

Benzyl

(2'-hydroxy-7'-phenyl-[1,1'-binaphthalen]-2-yl)carbamate

(3u):

1

450.1700.

(d, J = 9.2 Hz, 1H), 8.09 (d, J = 9.2 Hz, 1H), 8.02 (dd, J = 8.8, 4.4 Hz,

2H), 7.96 (d, J = 8.0 Hz, 1H), 7.68 (dd, J = 8.4, 2.0 Hz, 1H), 7.48 (t, J

= 8.0 Hz, 1H), 7.44-7.40 (m, 3H), 7.38-7.26 (m, 10H), 7.23 (d, J =

8.8 Hz, 1H), 6.61 (s, 1H), 5.27 (s, 1H), 5.10 (d, J = 12.4 Hz, 1H), 5.06

(d, J = 12.4 Hz, 1H). ¹³C NMR (100 MHz, CDCl₃) δ 153.7, 152.5,

141.0, 140.3, 135.9, 135.7, 133.5, 132.9, 131.0, 130.9, 130.5,

129.1, 128.7, 128.6, 128.6, 128.4, 128.3, 127.5, 127.5, 127.5,

127.4, 125.3, 125.1, 123.9, 122.0, 119.9, 118.0, 116.8, 113.0, 67.2.

HRMS (ESI) calcd for [M+H] C₃₄H₂₆NO₃, m/z: 496.1907, found:

496.1904.

Benzyl

(2'-hydroxy-6'-phenyl-[1,1'-binaphthalen]-2-yl)carbamate

(3q):

white solid, 84.1 mg, 85% yield. ¹H NMR (400 MHz, CDCl₃) δ 8.41

(d, J = 9.2 Hz, 1H), 7.98 (d, J = 2.0 Hz, 1H), 7.93 (d, J = 9.2 Hz, 1H),

7.89 (d, J = 8.8 Hz, 1H), 7.80 (d, J = 8.0 Hz, 1H), 7.55 (d, J = 7.6 Hz,

2H), 7.40 (dd, J = 8.8, 2.0 Hz, 1H), 7.36-7.29 (m, 3H), 7.28-7.22 (m,

2H), 7.20-7.11 (m, 6H), 7.05 (d, J = 8.8 Hz, 1H), 6.97 (d, J = 8.78 Hz,

1H), 6.43 (s, 1H), 5.18 (s, 1H), 4.93 (d, J = 12.0 Hz, 1H), 4.89 (d, J =

12.0 Hz, 1H). ¹³C NMR (100 MHz, CDCl₃) δ 153.7, 152.2, 140.9,

136.8, 135.9, 135.7, 133.0, 132.4, 131.6, 130.9, 130.4, 129.7,

128.9, 128.6, 128.4, 128.4, 128.3, 127.5, 127.3, 127.3, 127.1,

126.4, 125.3, 125.1, 124.8, 119.8, 118.5, 116.8, 112.7, 67.2. HRMS

(ESI) calcd for [M+H] C₃₄H₂₆NO₃, m/z: 496.1907, found: 496.1904.

Benzyl

Benzyl (7'-bromo-2'-hydroxy-[1,1'-binaphthalen]-2-yl)carbamate

1

(3v): white solid, 93.4 mg, 94% yield. H NMR (400 MHz, CDCl₃) δ

8.53 (d, J = 9.2 Hz, 1H), 8.08 (d, J = 9.2 Hz, 1H), 7.95 (d, J = 8.0 Hz,

1H), 7.94 (d, J = 9.2 Hz, 1H), 7.78 (d, J = 8.8 Hz, 1H), 7.49-7.45 (m,

2H), 7.39 (d, J = 9.2 Hz, 1H), 7.37-7.28 (m, 6H), 7.18 (d, J = 2.0 Hz,

1H), 7.10 (d, J = 8.8 Hz, 1H), 6.47 (s, 1H), 5.39 (s, 1H), 5.09 (d, J =

12.4 Hz, 1H), 5.05 (d, J = 12.0 Hz, 1H). ¹³C NMR (100 MHz, CDCl₃) δ

153.6, 153.0, 135.9, 135.6, 134.6, 132.8, 131.2, 130.9, 130.7,

130.1, 128.6, 128.4, 128.4, 128.4, 127.9, 127.6, 127.5, 126.1,

125.4, 124.9, 122.2, 119.9, 118.5, 116.2, 112.2, 67.3. HRMS (ESI)

calcd for [M+H] C₂₈H₂₁BrNO₃, m/z: 498.0699, found: 498.0702.

Benzyl

(6'-bromo-2'-hydroxy-[1,1'-binaphthalen]-2-yl)carbamate

(3r):

white solid, 85.5 mg, 86% yield. ¹H NMR (400 MHz, CDCl₃) δ 8.51

(d, J = 9.2 Hz, 1H), 8.08 (s, 1H), 8.07 (d, J = 8.4 Hz, 1H), 7.94 (d, J =

8.4 Hz, 1H), 7.89 (d, J = 8.8 Hz, 1H), 7.46 (t, J = 7.2 Hz, 1H), 7.40 (d,

J = 8.8 Hz, 1H), 7.36-7.26 (m, 7H), 7.10 (d, J = 8.4 Hz, 1H), 6.91 (d, J

= 8.8 Hz, 1H), 6.46 (s, 1H), 5.36 (s, 1H), 5.08 (d, J = 12.0 Hz, 1H),

5.03 (d, J = 12.4 Hz, 1H). ¹³C NMR (100 MHz, CDCl₃) δ 153.6, 152.4,

135.8, 135.6, 132.8, 131.8, 130.8, 130.7, 130.6, 130.5, 130.4,

130.3, 128.6, 128.4, 128.4, 128.4, 127.5, 126.0, 125.4, 124.9,

(1-(10-hydroxyphenanthren-9-yl)naphthalen-2-yl)carbamate (3w):

pale yellow solid, 85.4 mg, 91% yield. ¹H NMR (400 MHz, CDCl₃) δ

119.8, 119.2, 117.8, 116.3, 113.1, 67.2. HRMS (ESI) calcd for [M+H] 8.67 (d, J = 8.4 Hz, 1H), 8.61 (d, J = 8.4 Hz, 1H), 8.45 (d, J = 8.8 Hz,

C₂₈H₂₁BrNO₃, m/z: 498.0699, found: 498.0694.

Benzyl

1H), 8.34 (dd, J = 8.0, 1.6 Hz, 1H), 7.95 (d, J = 9.2 Hz, 1H), 7.80 (d, J

= 8.0 Hz, 1H), 7.69-7.65 (m, 1H), 7.61-7.57 (m, 1H), 7.41-7.37 (m,

1H), 7.31-7.27 (m, 1H), 7.23-7.18 (m, 1H), 7.15-7.05 (m, 7H), 6.92

(dd, J = 8.0, 1.2 Hz, 1H), 6.51 (s, 1H), 5.46 (s, 1H), 4.86 (d, J = 12.0

Hz, 1H), 4.81 (d, J = 12.0 Hz, 1H). ¹³C NMR (100 MHz, CDCl₃) δ

153.6, 148.4, 136.3, 135.7, 133.0, 132.0, 131.6, 130.9, 130.6,

128.5, 128.4, 128.4, 128.3, 128.1, 127.7, 127.5, 127.1, 126.9,

125.4, 125.2, 125.1, 124.8, 124.8, 123.6, 123.0, 122.8, 119.7,

116.7, 108.9, 67.1. HRMS (ESI) calcd for [M+H] C₃₂H₂₄NO₃, m/z:

(6'-fluoro-2'-hydroxy-[1,1'-binaphthalen]-2-yl)carbamate

(3s):

1

white solid, 72.5 mg, 83% yield. H NMR (400 MHz, DMSO-d₆) δ

8.52 (d, J = 9.2 Hz, 1H), 8.07 (d, J = 8.8 Hz, 1H), 7.94 (d, J = 7.6 Hz,

1H), 7.91 (d, J = 9.2 Hz, 1H), 7.54 (dd, J = 7.6, 2.4 Hz, 1H), 7.46 (t, J

= 7.6 Hz, 1H), 7.42 (d, J = 8.8 Hz, 1H), 7.35-7.26 (m, 6H), 7.12 (d,

J = 8.4 Hz, 1H), 7.08-6.99 (m, 2H), 6.49 (s, 1H), 5.24 (s, 1H), 5.06

(dd, J = 18.8, 12.0 Hz, 2H). ¹³C NMR (100 MHz, DMSO-d₆) δ 159.7

Chin. J. Chem. 2019, 37, XXX－XXX

www.cjc.wiley-vch.de

Zhang et al.

Report

470.1751, found: 470.1753.

2'-(((benzyloxy)carbonyl)amino)-2-hydroxy-6'-methoxy-[1,1'-bina

phthalene] -6-carboxylate (3ab): pale yellow solid, 86.2 mg, 85%

yield. ¹H NMR (400 MHz, CDCl₃) δ 8.62 (d, J = 2.0 Hz, 1H), 8.38 (d, J

= 8.8 Hz, 1H), 8.04 (d, J = 9.2 Hz, 1H), 7.92 (d, J = 8.8 Hz, 1H), 7.81

(dd, J = 8.8, 1.6 Hz, 1H), 7.42 (d, J = 8.8 Hz, 1H), 7.33-7.28 (m, 3H),

7.25-7.22 (m, 2H), 7.20 (d, J = 2.4 Hz, 1H), 7.05 (d, J = 8.8 Hz, 1H),

7.02-6.94 (m, 2H), 6.45 (s, 1H), 5.93 (s, 1H), 5.04 (d, J = 12.4 Hz,

1H), 5.00 (d, J = 12.0 Hz, 1H), 3.94 (s, 3H), 3.88 (s, 3H). ¹³C NMR

(100 MHz, CDCl₃) δ 167.2, 157.3, 154.2, 153.8, 135.8, 135.7, 133.7,

132.5, 132.2, 131.5, 129.1, 128.5, 128.3, 128.3, 128.2, 128.1,

126.8, 126.6, 125.4, 124.3, 121.0, 120.0, 119.0, 117.6, 113.4,

106.5, 67.1, 55.4, 52.2. HRMS (ESI) calcd for [M+H] C₃₁H₂₆NO₆,

m/z: 508.1755, found: 508.1749.

Benzyl

(2'-hydroxy-6,6'-diphenyl-[1,1'-binaphthalen]-2-yl)carbamate (3x):

white solid, 100.5 mg, 88% yield. ¹H NMR (400 MHz, CDCl₃) δ 8.61

(d, J = 9.2 Hz, 1H), 8.17-8.14 (m, 3H), 8.08 (d, J = 9.2 Hz, 1H),

7.74-7.71 (m, 4H), 7.62-7.58 (m, 2H), 7.53-7.49 (m, 4H), 7.46 (d, J

= 8.8 Hz, 1H), 7.43-7.39 (m, 2H), 7.35-7.27 (m, 6H), 7.18 (d, J = 8.8

Hz, 1H), 6.62 (s, 1H), 5.38 (s, 1H), 5.10 (d, J = 12.4 Hz, 1H), 5.06 (d,

J = 12.0 Hz, 1H). ¹³C NMR (100 MHz, CDCl₃) δ 153.6, 152.2, 140.8,

140.7, 138.0, 136.8, 135.9, 135.7, 132.4, 132.2, 131.6, 131.1,

130.7, 129.7, 129.0, 128.9, 128.6, 128.4, 128.4, 127.5, 127.3,

127.3, 127.3, 127.1, 127.1, 126.4, 126.2, 125.7, 124.8, 120.2,

118.5, 116.7, 112.6, 67.2. HRMS (ESI) calcd for [M+H] C₄₀H₃₀NO₃,

m/z: 572.2220, found: 572.2223.

Benzyl

(7'-bromo-2'-hydroxy-6-methoxy-[1,1'-binaphthalen]-2-yl)carbam

ate (3ac): white solid, 90.6 mg, 86% yield. ¹H NMR (400 MHz,

CDCl₃) δ 8.43 (d, J = 8.8 Hz, 1H), 7.97 (d, J = 8.8 Hz, 1H), 7.92 (d, J =

9.2 Hz, 1H), 7.76 (d, J = 8.8 Hz, 1H), 7.46 (dd, J = 8.8, 2.0 Hz, 1H),

7.37 (d, J = 9.2 Hz, 1H), 7.35-7.25 (m, 6H), 7.16 (d, J = 2.4 Hz, 1H),

7.00 (d, J = 1.6 Hz, 2H), 6.35 (s, 1H), 5.27 (s, 1H), 5.11 (d, J = 12.0

Hz, 1H), 5.07 (d, J = 12.4 Hz, 1H), 3.94 (s, 3H). ¹³C NMR (100 MHz,

CDCl₃) δ 157.4, 153.8, 152.8, 135.7, 134.5, 133.8, 132.2, 131.1,

130.1, 129.4, 128.6, 128.4, 128.3, 128.0, 127.8, 127.5, 126.5,

126.1, 122.1, 120.8, 120.2, 118.4, 116.8, 112.5, 106.5, 67.2, 55.4.

HRMS (ESI) calcd for [M+H] C₂₉H₂₃BrNO₄, m/z: 528.0805, found:

528.0803.

(6,6'-dibromo-2'-hydroxy-[1,1'-binaphthalen]-2-yl)carbamate (3y):

white solid, 98.9 mg, 86% yield. H NMR (400 MHz, CDCl₃) δ 8.56

1

(d, J = 9.2 Hz, 1H), 8.09 (d, J = 2.0 Hz, 1H), 8.07 (d, J = 2.0 Hz, 1H),

7.98 (d, J = 9.2 Hz, 1H), 7.90 (d, J = 8.8 Hz, 1H), 7.40-7.32 (m, 6H),

7.28-7.26 (m, 2H), 6.94 (d, J = 9.2 Hz, 1H), 6.84 (d, J = 8.8 Hz, 1H),

6.42 (s, 1H), 5.10 (s, 1H), 5.10 (d, J = 12.4 Hz, 1H), 5.07 (d, J = 12.0

Hz, 1H). ¹³C NMR (100 MHz, CDCl₃) δ 153.4, 152.3, 136.2, 135.5,

131.8, 131.6, 131.3, 130.8, 130.8, 130.6, 130.5, 130.5, 130.3,

129.6, 128.6, 128.5, 128.4, 126.6, 125.7, 120.8, 119.4, 119.1,

118.0, 116.2, 112.4, 67.4. HRMS (ESI) calcd for [M+H]

C₂₈H₂₀Br₂NO₃, m/z: 575.9804, found: 575.9801.

Benzyl

Methyl

(6,6'-difluoro-2'-hydroxy-[1,1'-binaphthalen]-2-yl)carbamate (3z):

pale yellow solid, 71.0 mg, 78% yield. ¹H NMR (400 MHz, CDCl₃) δ

8.51 (d, J = 9.2 Hz, 1H), 7.99 (d, J = 9.2 Hz, 1H), 7.91 (d, J = 9.2 Hz,

1H), 7.54 (dd, J = 9.6, 3.2 Hz, 2H), 7.40 (d, J = 8.8 Hz, 1H),

7.36-7.31 (m, 3H), 7.29-7.25 (m, 2H), 7.09 (d, J = 6.4 Hz, 2H), 7.05

(dd, J = 8.4, 2.8 Hz, 1H), 6.99-6.95 (m, 1H), 6.43 (s, 1H), 5.20 (s,

1H), 5.08 (d, J = 12.0 Hz, 1H), 5.04 (d, J = 12.0 Hz, 1H). ¹⁹F NMR

(376 MHz, CDCl₃) δ -115.68, -117.81. ¹³C NMR (100 MHz, CDCl₃) δ

160.3 (d, J = 245.0 Hz), 159.6 (d, J = 243.2 Hz, 1H), 153.6, 151.4 (d,

J = 2.6 Hz, 1H), 135.6, 135.2 (d, J = 2.5 Hz, 1H), 131.6 (d, J = 9.1 Hz,

2-(((benzyloxy)carbonyl)amino)-7'-bromo-2'-hydroxy-[1,1'-binaph

thalene]-6-carboxylate (3ad): white solid, 91.0 mg, 82% yield. H

1

NMR (400 MHz, CDCl₃) δ 8.61 (d, J = 9.2 Hz, 1H), 8.38 (d, J = 1.6 Hz,

1H), 8.03 (d, J = 9.2 Hz, 1H), 7.95 (d, J = 9.2 Hz, 1H), 7.78-7.74 (m,

2H), 7.46 (dd, J = 8.4, 2.0 Hz, 1H), 7.42 (d, J = 8.8 Hz, 1H),

7.37-7.27 (m, 5H), 7.10-7.08 (m, 2H) 6.61 (s, 1H), 6.28 (s, 1H), 5.09

(d, J = 12.4 Hz, 1H), 5.04 (d, J = 12.4 Hz, 1H), 3.86 (s, 3H). ¹³C NMR

(100 MHz, CDCl₃) δ 167.1, 153.4, 153.3, 138.1, 135.5, 135.3, 134.5,

131.9, 131.5, 131.3, 130.2, 129.6, 128.6, 128.5, 128.4, 127.8,

127.5, 126.7, 126.3, 125.8, 125.1, 122.2, 119.9, 118.9, 116.1,

1H), 130.5 (d, J = 5.1 Hz, 1H), 130.0 (d, J = 9.1 Hz, 1H), 129.9, 129.8, 111.4, 67.4, 52.3. HRMS (ESI) calcd for [M+H] C₃₀H₂₃BrNO₅, m/z:

129.6 (d, J = 5.1 Hz, 1H), 128.6, 128.5, 128.3, 127.5 (d, J = 8.8 Hz,

1H), 126.3 (d, J = 8.4 Hz, 1H), 121.2, 119.2, 117.7 (d, J = 24.8 Hz,

1H), 1176 (d, J = 24.8 Hz, 1H), 117.3, 112.9, 116.8 (d, J = 20.8 Hz,

1H), 116.5 (d, J = 20.4 Hz, 1H), 67.3. HRMS (ESI) calcd for [M+H]

C₂₈H₂₀F₂NO₃, m/z: 456.1406, found: 456.1400.

556.0754, found: 556.0751.

Benzyl

(2'-hydroxy-7,7'-diphenyl-[1,1'-binaphthalen]-2-yl)carbamate

(3ae): white solid, 95.9 mg, 84% yield. ¹H NMR (400 MHz, CDCl₃) δ

8.58 (d, J = 8.8 Hz, 1H), 8.12 (d, J = 9.2 Hz, 1H), 8.05 (s, 1H), 8.03 (d,

J = 8.4 Hz, 1H), 8.03 (s, 1H), 7.75 (dd, J = 8.4, 2.0 Hz, 1H), 7.69 (dd,

J = 8.4, 2.0 Hz, 1H), 7.46-7.42 (m, 6H), 7.38-7.27 (m, 12H), 6.63 (s,

1H), 5.35 (s, 1H), 5.12 (d, J = 12.4 Hz, 1H), 5.10 (d, J = 12.0 Hz, 1H).

Dimethyl

2-(((benzyloxy)carbonyl)amino)-2'-hydroxy-[1,1'-binaphthalene]-6

1

,6'-dicarboxylate (3aa): white solid, 86.7 mg, 81% yield. H NMR

(400 MHz, CDCl₃) δ 8.59 (s, 1H),8.58 (d, J = 8.0 Hz, 1H), 8.36 (s, 1H), ¹³C NMR (100 MHz, CDCl₃) δ 153.7, 152.5, 141.0, 141.0, 140.4,

8.06 (dd, J = 9.2, 2.4 Hz, 1H), 7.99 (dd, J = 9.2, 2.8 Hz, 1H),

7.82-7.78 (m, 1H), 7.74-7.70 (m, 1H), 7.47 (dd, J = 8.8, 2.4 Hz, 1H),

7.31-7.23 (m, 5H), 7.09 (dd, J = 8.8, 2.4 Hz, 1H), 6.97 (dd, J = 8.8,

2.4 Hz, 1H), 6.62 (s, 2H), 5.04 (s, 2H), 3.92 (s, 3H), 3.84 (s, 3H). ¹³C

NMR (100 MHz, CDCl₃) δ 167.2, 167.0, 154.8, 153.3, 138.0, 135.7,

135.4, 135.3, 132.9, 131.7, 131.6, 131.2, 129.5, 128.6, 128.5,

128.4, 127.0, 126.6, 126.3, 126.2, 125.5, 125.1, 124.0, 120.0,

119.4, 116.5, 112.3, 67.3, 52.3, 52.2. HRMS (ESI) calcd for [M+H]

C₃₂H₂₆NO₇, m/z: 536.1704, found: 536.1698.

140.3, 136.4, 135.7, 133.5, 133.2, 131.2, 130.2, 130.1, 129.1,

129.0, 128.8, 128.8, 128.7, 128.6, 128.4, 128.3, 127.5, 127.5,

127.4, 127.4, 125.3, 123.9, 122.9, 121.9, 120.0, 118.0, 117.1,

112.9, 67.2. HRMS (ESI) calcd for [M+H] C₄₀H₃₀N, m/z: 572.2220,

found: 572.2220.

Benzyl

(7,7'-dibromo-2'-hydroxy-[1,1'-binaphthalen]-2-yl)carbamate (3af):

pale yellow solid, 94.1 mg, 82% yield. ¹H NMR (400 MHz, CDCl₃) δ

8.53 (d, J = 9.2 Hz, 1H), 8.01 (d, J = 9.2 Hz, 1H), 7.94 (d, J = 8.8 Hz,

1H), 7.79 (d, J = 9.2 Hz, 1H), 7.79 (d, J = 8.8 Hz, 1H), 7.53 (d, J = 8.8

Methyl

www.cjc.wiley-vch.de

Chin. J. Chem. 2019, 37, XXX－XXX

Running title

Chin. J. Chem.

Hz, 1H), 7.49 (d, J = 8.8 Hz, 1H), 7.38-7.27 (m, 6H), 7.22 (s, 1H),

7.13 (s, 1H), 6.44 (s, 1H), 5.43 (s, 1H), 5.08 (d, J = 12.4 Hz, 1H),

5.03 (d, J = 12.0 Hz, 1H). ¹³C NMR (100 MHz, CDCl₃) δ 153.4, 153.0,

136.8, 135.5, 134.4, 134.2, 131.6, 130.6, 130.3, 130.1, 129.2,

128.9, 128.6, 128.5, 128.4, 127.9, 127.7, 126.8, 125.8, 122.4,

122.2, 120.1, 118.6, 115.4, 111.3, 67.4. HRMS (ESI) calcd for

[M+Na] C₂₈H₁₉Br₂NNaO₃, m/z: 597.9624, found: 597.9621.

Benzyl

(2'-(naphthalen-2-yloxy)-[1,1'-binaphthalen]-2-yl)carbamate (5a):

white solid, 103.6 mg, 95% yield. ¹H NMR (400 MHz, CDCl₃) δ 8.41

(s, 1H), 8.05 (d, J = 8.8 Hz, 1H), 8.01-7.96 (m, 2H), 7.88 (d, J = 8.0

Hz, 1H), 7.76 (d, J = 8.0 Hz, 1H), 7.65 (d, J = 8.8 Hz, 1H), 7.58 (d, J =

7.6 Hz, 1H), 7.52 (t, J = 8.0 Hz, 1H), 7.45-7.21 (m, 14H), 7.03 (d, J =

8.8 Hz, 1H), 6.63 (s, 1H), 5.06 (s, 2H). ¹³C NMR (100 MHz, DMSO-d₆)

δ 154.8, 154.6, 152.9, 137.1, 135.4, 134.3, 134.1, 133.1, 131.0,

131.0, 130.9, 130.1, 130.1, 128.8, 128.8, 128.8, 128.4, 128.2,

128.0, 128.0, 128.0, 127.4, 127.4, 127.0, 126.8, 125.9, 125.5,

125.3, 125.1, 123.5, 123.3, 121.7, 120.1, 119.6, 114.4, 66.0. HRMS

(7-bromo-2'-hydroxy-7'-phenyl-[1,1'-binaphthalen]-2-yl)carbamat

e (3ag): white solid, 92.8 mg, 81% yield. ¹H NMR (400 MHz, CDCl₃)

δ 8.57 (d, J = 9.2 Hz, 1H), 8.04-8.01 (m, 3H), 7.80 (d, J = 8.8 Hz, 1H), (ESI) calcd for [M+H] C₃₈H₂₈NO₃, m/z: 546.2064, found: 546.2069.

7.69 (dd, J = 8.4, 2.0 Hz, 1H), 7.54 (dd, J = 8.4, 2.0 Hz, 1H),

7.45-7.30 (m, 10H), 7.27-7.25 (m, 2H), 7.20 (d, J = 2.0 Hz, 1H), 6.58

(s, 1H), 5.28 (s, 1H), 5.09 (d, J = 12.0 Hz, 1H), 5.05 (d, J = 12.0 Hz,

Ethyl

(2'-(naphthalen-2-yloxy)-[1,1'-binaphthalen]-2-yl)carbamate (5b):

1

white solid, 87.9 mg, 91% yield. H NMR (400 MHz, CDCl₃) δ 8.40

1H). ¹³C NMR (100 MHz, CDCl₃) δ 153.6, 152.5, 140.9, 140.5, 136.8, (s, 1H), 8.06 (d, J = 8.8 Hz, 1H), 8.00 (d, J = 7.6 Hz, 1H), 7.95 (d, J =

135.6, 134.3, 133.3, 131.4, 130.3, 130.0, 129.3, 129.2, 128.8,

128.8, 128.7, 128.6, 128.4, 128.3, 127.5, 127.5, 127.0, 124.1,

122.1, 121.6, 120.1, 118.1, 116.1, 112.2, 67.3. HRMS (ESI) calcd

for [M+H] C₃₄H₂₅BrNO₃, m/z: 574.1012, found: 574.1010.

Benzyl

9.2 Hz, 1H), 7.86 (d, J = 8.0 Hz, 1H), 7.75 (d, J = 8.0 Hz, 1H), 7.68 (d,

J = 8.8 Hz, 1H), 7.61 (d, J = 8.0 Hz, 1H), 7.53-7.49 (m, 1H), 7.45 (d, J

= 8.8 Hz, 1H), 7.42-7.34 (m, 4H), 7.28-7.21 (m, 3H), 7.19 (d, J = 8.0

Hz, 1H), 7.03 (dd, J = 9.2, 2.8 Hz, 1H), 6.51 (s, 1H), 4.05 (q, J = 7.2

Hz, 2H), 1.19 (t, J = 7.2 Hz, 3H). ¹³C NMR (100 MHz, CDCl₃) δ 155.0,

153.7, 153.0, 134.7, 134.1, 134.0, 133.1, 130.9, 130.9, 130.5,

130.1, 129.8, 129.2, 128.4, 128.1, 127.7, 127.6, 127.1, 126.5,

126.5, 125.6, 125.6, 125.6, 124.7, 124.6, 121.4, 120.0, 119.8,

119.7, 119.5, 113.9, 61.3, 14.5. HRMS (ESI) calcd for [M+H]

C₃₃H₂₆NO₃, m/z: 484.1907, found: 484.1912.

N-(2'-(naphthalen-2-yloxy)-[1,1'-binaphthalen]-2-yl)-P,P-diphe

nylphosphinic amide (5c): white solid, 102.6 mg, 84% yield: ¹H

NMR (400 MHz, CDCl₃) δ 7.99 (d, J = 8.8 Hz, 1H), 7.95 (d, J = 8.0 Hz,

1H), 7.73-7.60 (m, 9H), 7.49 (t, J = 7.6 Hz, 2H), 7.42-7.32 (m, 6H),

7.30-7.18 (m, 9H), 7.06 (dd, J = 8.8, 2.4 Hz, 1H), 5.39 (d, J = 10.0 Hz,

1H). ³¹P NMR (162 MHz, CDCl₃) δ 17.51. ¹³C NMR (100 MHz, CDCl₃)

δ 154.9, 152.9, 137.2, 134.1, 133.8, 133.5, 133.0, 132.7, 132.2,

132.1, 132.0, 131.7, 131.6, 131.5, 131.4, 131.0, 130.9, 130.1,

129.9, 129.6, 129.3, 128.8, 128.7, 128.7, 128.6, 128.4, 128.1,

127.7, 127.5, 127.0, 126.6, 126.5, 126.0, 125.7, 125.1, 124.8,

123.8, 121.9, 119.7, 119.5, 119.4, 119.3, 118.6, 118.5, 113.9. (Due

to C-P coupling and the complexity of the spectrum, doublets in

the aromatic region cannot be assigned and they are listed as

singlets.) HRMS (ESI) calcd for [M+H] C₄₂H₃₁NO₂P, m/z: 612.2087,

found: 612.2087.

4-methyl-N-(2'-(naphthalen-2-yloxy)-[1,1'-binaphthalen]-2-yl)

benzenesulfonamide (5d): white solid, 101.7 mg, 90% yield. ¹H

NMR (400 MHz, DMSO-d₆) δ 9.24 (s, 1H), 8.13 (d, J = 9.2 Hz, 1H),

8.05 (d, J = 7.2 Hz, 1H), 7.90 (d, J = 9.2 Hz, 1H), 7.84 (t, J = 6.0 Hz,

2H), 7.81 (d, J = 9.2 Hz, 1H), 7.71 (d, J = 8.4 Hz, 1H), 7.62 (d, J = 9.2

Hz, 1H), 7.55-7.53 (m, 2H), 7.49-7.42 (m, 3H), 7.40 (d, J = 8.4, 1.6

Hz, 1H), 7.36 (d, J = 8.4 Hz, 1H), 7.32 (d, J = 9.2 Hz, 1H), 7.28-7.24

(m, 2H), 7.16 (dd, J = 8.8, 2.4 Hz, 1H), 7.10 (d, J = 8.4 Hz, 2H), 7.04

(d, J = 8.0 Hz, 1H), 6.80 (d, J = 8.0 Hz, 1H), 2.26 (s, 3H). ¹³C NMR

(100 MHz, DMSO-d₆) δ 154.8, 153.1, 143.4, 138.3, 134.6, 134.3,

134.1, 133.3, 131.1, 130.8, 130.7, 130.1, 130.1, 129.9, 129.3,

128.6, 128.3, 128.0, 127.4, 127.3, 127.1, 127.0, 127.0, 125.9,

125.4, 125.4, 125.1, 125.1, 123.2, 121.3, 120.7, 120.2, 119.7,

114.5, 21.4. HRMS (ESI) calcd for [M+H] C₃₇H₂₈NO₃S, m/z:

566.1784, found: 566.1780.

(7'-bromo-2'-hydroxy-7-methoxy-[1,1'-binaphthalen]-2-yl)carbam

ate (3ah): white solid, 95.9 mg, 91% yield. ¹H NMR (400 MHz,

CDCl₃) δ 8.37 (d, J = 9.2 Hz, 1H), 7.98 (d, J = 9.2 Hz, 1H), 7.93 (d, J =

8.8 Hz, 1H), 7.84 (d, J = 8.8 Hz, 1H), 7.77 (d, J = 8.8 Hz, 1H), 7.47

(dd, J = 8.4, 2.0 Hz, 1H), 7.39 (d, J = 8.8 Hz, 1H), 7.35-7.27 (m, 5H),

7.23 (d, J = 2.4 Hz, 1H), 7.13 (dd, J = 8.8, 2.4 Hz, 1H), 6.43 (s, 1H),

6.37 (d, J = 2.8 Hz, 1H), 5.44 (s, 1H), 5.09 (d, J = 12.4 Hz, 1H), 5.04

(d, J = 12.0 Hz, 1H), 3.54 (s, 3H). ¹³C NMR (100 MHz, CDCl₃) δ

159.0, 153.5, 152.9, 136.5, 135.7, 134.4, 134.2, 131.2, 130.4,

130.1, 130.0, 128.6, 128.4, 128.3, 127.9, 127.5, 126.3, 126.0,

122.1, 118.5, 117.5, 117.4, 114.8, 112.3, 103.7, 67.2, 55.1. HRMS

(ESI) calcd for [M+H] C₂₉H₂₃BrNO₄, m/z: 528.0805, found:

528.0802.

Benzyl

(1-(10-hydroxyphenanthren-9-yl)-7-methoxynaphthalen-2-yl)carb

1

amate (3ai) : pale yellow solid, 88.8 mg, 89% yield. H NMR (400

MHz, CDCl₃) δ 8.85 (d, J = 8.4 Hz, 1H), 8.78 (d, J = 8.0 Hz, 1H), 8.53

(dd, J = 8.4, 1.6 Hz, 1H), 8.48 (d, J = 8.8 Hz, 1H), 8.04 (d, J = 9.2 Hz,

1H), 7.88-7.83 (m, 2H), 7.77 (t, J = 7.2 Hz, 1H), 7.60-7.56 (m, 1H),

7.43-7.39 (m, 1H), 7.32-7.29 (m, 3H), 7.26-7.23 (m, 2H), 7.17-7.12

(m, 2H), 6.65 (s, 1H), 5.70 (d, J = 2.4 Hz, 1H), 5.05 (d, J = 12.0 Hz,

1H), 5.05 (d, J = 12.0 Hz, 1H), 5.01 (d, J = 12.4 Hz, 1H), 3.46 (s, 3H).

¹³C NMR (100 MHz, CDCl₃) δ 159.0, 153.6, 148.3, 136.8, 135.8,

134.5, 132.0, 131.4, 130.3, 130.0, 128.5, 128.3, 128.3, 128.0,

127.7, 127.1, 126.8, 126.3, 125.1, 124.8, 124.8, 123.7, 123.0,

122.8, 117.6, 117.3, 115.5, 109.1, 103.9, 67.1, 55.1. HRMS (ESI)

calcd for [M+H] C₃₃H₂₆NO₄, m/z: 500.1856, found: 500.1851.

II. General procedures for synthesis of NOBIN derivatives 5.

Compound 4 (0.20 mmol), 2 (0.44 mmol) and Cs₂CO₃(97.8 mg,

0.30 mmol) were added to a bottle with a stirring bar. Toluene (4

mL) was added and the reaction mixture was stirred for 12 h at

room temperature till 4 was completely consumed (monitored by

TLC). After evaporated the solvent, the residue was purified by

flash chromatography eluted with PE/DCM = 1/1 to afford the

corresponding product 5.

Benzyl

(6'-methoxy-2'-(naphthalen-2-yloxy)-[1,1'-binaphthalen]-2-yl)carb

Benzyl

Chin. J. Chem. 2019, 37, XXX－XXX

www.cjc.wiley-vch.de

Zhang et al.

Report

1

amate (5e): white solid, 109.3 mg, 95% yield. H NMR (400 MHz,

CDCl₃) δ 8.43 (s, 1H), 7.97 (dd, J = 8.8, 3.2 Hz, 2H), 7.87 (d, J = 7.9

Hz, 1H), 7.75 (d, J = 7.8 Hz, 1H), 7.64 (d, J = 8.0 Hz, 1H), 7.58 (d, J =

7.6 Hz, 1H), 7.50-7.16 (m, 14H), 7.07-7.01 (m, 2H), 6.66 (s, 1H),

1H), 7.92 (d, J = 8.4 Hz, 1H), 7.84 (d, J = 8.8 Hz, 1H), 7.80 (d, J = 8.0

Hz, 1H), 7.69 (d, J = 8.8 Hz, 1H), 7.62 (t, J = 9.2 Hz, 2H), 7.49-7.34

(m, 11H), 7.28-7.26 (m, 2H), 7.06 (d, J = 9.2 Hz, 1H), 6.67 (s, 1H),

5.14 (s, 2H). ¹³C NMR (100 MHz, CDCl₃) δ 154.4, 154.1, 153.5,

5.07 (s, 2H), 3.97 (s, 3H). ¹³C NMR (100 MHz, CDCl₃) δ 157.5, 155.3, 136.0, 135.3, 134.6, 134.1, 133.0, 131.0, 130.7, 130.3, 130.2,

153.5, 151.1, 136.1, 134.4, 134.1, 133.0, 132.2, 130.5, 129.9,

129.7, 129.6, 129.2, 129.1, 128.6, 128.3, 128.3, 128.1, 127.7,

127.1, 127.0, 126.5, 126.4, 125.6, 124.6, 124.5, 121.7, 120.8,

120.1, 119.8, 119.5, 119.3, 113.4, 106.7, 67.0, 55.4. HRMS (ESI)

calcd for [M+H] C₃₉H₃₀NO₄, m/z: 576.2169, found: 576.2163.

Benzyl

130.0, 129.6, 129.3, 129.1, 128.7, 128.4, 128.4, 128.3, 127.8,

127.3, 127.2, 126.8, 126.7, 125.3, 125.0, 124.9, 122.4, 120.6,

120.3, 120.0, 119.9, 119.8, 114.6, 67.2. HRMS (ESI) calcd for [M+H]

C₃₈H₂₇BrNO₃, m/z: 624.1169, found: 624.1169.

Benzyl

(6-phenyl-2'-((6-phenylnaphthalen-2-yl)oxy)-[1,1'-

binaphthalen]-2-yl)carbamate (5j): white solid, 97.6 mg, 70% yield.

¹H NMR (400 MHz, CDCl₃) δ 8.46 (s, 1H), 8.09 (d, J = 9.2 Hz, 1H),

8.06 (d, J = 2.0 Hz, 1H), 8.04 (s, 1H), 8.02 (s, 1H), 7.94 (d, J = 1.6 Hz,

1H), 7.71-7.62 (m, 7H), 7.56-7.45 (m, 7H), 7.42-7.35 (m, 6H),

7.33-7.31 (m, 3H), 7.27 (d, J = 8.0 Hz, 1H), 7.23 (d, J = 2.8 Hz, 1H),

7.05 (dd, J = 8.8, 2.4 Hz, 1H), 6.66 (s, 1H), 5.09 (s, 2H).¹³C NMR

(100 MHz, CDCl₃) δ 155.0, 153.5, 153.0, 141.0, 140.9, 137.4, 137.3,

136.0, 134.6, 134.0, 133.2, 132.2, 131.0, 131.0, 130.8, 130.3,

130.0, 129.5, 128.9, 128.8, 128.6, 128.4, 128.4, 128.3, 128.3,

127.6, 127.6, 127.3, 127.3, 127.3, 127.2, 126.2, 126.1, 125.9,

125.6, 125.6, 125.5, 121.2, 120.3, 120.1, 120.0, 119.8, 113.8, 67.0.

HRMS (ESI) calcd for [M+H] C₅₀H₃₆NO₃, m/z: 698.2690, found:

698.2691.

(6'-methyl-2'-(naphthalen-2-yloxy)-[1,1'-binaphthalen]-2-yl)carba

1

mate (5f): white solid, 104.0 mg, 93% yield. H NMR (400 MHz,

CDCl₃) δ 8.47 (s, 1H), 8.00 (d, J = 9.2 Hz, 1H), 7.99 (d, J = 8.8 Hz,

1H), 7.90 (d, J = 8.0 Hz, 1H), 7.80 (s, 1H), 7.78 (d, J = 8.8 Hz, 1H),

7.66 (d, J = 8.8 Hz, 1H), 7.60 (d, J = 7.6 Hz, 1H), 7.46-7.37 (m, 7H),

7.35-7.27 (m, 4H), 7.23 (dd, J = 8.8, 2.4 Hz, 2H), 7.20 (s, 1H), 7.05

(dd, J = 9.2, 2.8 Hz, 1H), 6.70 (s, 1H), 5.09 (s, 2H), 2.57 (s, 3H). ¹³C

NMR (100 MHz, CDCl₃) δ 155.1, 153.5, 152.3, 136.1, 135.3, 134.5,

134.1, 133.1, 132.1, 131.2, 130.6, 130.3, 130.0, 129.8, 129.7,

129.2, 128.6, 128.3, 128.3, 128.1, 127.7, 127.5, 127.1, 126.5,

126.5, 125.6, 125.4, 124.6, 124.6, 121.2, 120.3, 120.1, 119.8,

119.6, 113.7, 67.0, 21.6. HRMS (ESI) calcd for [M+H] C₃₉H₃₀NO₃,

m/z: 560.2220, found: 560.2217.

Benzyl

Methyl

2'-(((benzyloxy)carbonyl)amino)-2-(naphthalen-2-

(6-fluoro-2'-((6-fluoronaphthalen-2-yl)oxy)-[1,1'-binaphthalen]-2-

yl)carbamate (5k): white solid, 104.6 mg, 90% yield. H NMR (400

1

yloxy)-[1,1'-binaphthalene]-6-carboxylate (5g): white solid, 109.7

mg, 91% yield. ¹H NMR (400 MHz, CDCl₃) δ 8.75 (d, J = 2.0 Hz, 1H),

8.43 (s, 1H), 8.12 (d, J = 9.2 Hz, 1H), 8.00 (d, J = 9.2 Hz, 1H),

7.93-7.89 (m, 2H), 7.78-7.76 (m, 1H), 7.68 (d, J = 8.8 Hz, 1H),

7.61-7.59 (m, 1H), 7.46-7.38 (m, 4H), 7.37-7.26 (m, 8H), 7.19 (d, J

= 8.4 Hz, 1H), 7.04 (dd, J = 9.2, 2.8 Hz, 1H), 6.60 (s, 1H), 5.10 (d, J =

12.0 Hz, 1H), 5.06 (d, J = 12.4 Hz, 1H), 4.00 (s, 3H). ¹³C NMR (100

MHz, CDCl₃) δ 167.0, 155.2, 154.1, 153.5, 136.3, 135.9, 134.5,

134.1, 132.9, 132.3, 131.5, 130.7, 130.4, 130.0, 129.8, 129.5,

128.6, 128.4, 128.3, 128.2, 127.7, 127.1, 127.0, 126.9, 126.7,

126.6, 125.6, 125.3, 125.0, 124.8, 120.8, 120.0, 119.9, 119.8,

119.5, 67.0, 52.3, 114.9. HRMS (ESI) calcd for [M+H] C₄₀H₃₀NO₅,

m/z: 604.2118, found: 604.2113.

MHz, CDCl₃) δ 8.40 (s, 1H), 8.04 (d, J = 8.8 Hz, 1H), 7.98 (d, J = 8.0

Hz, 1H), 7.86 (d, J = 9.2 Hz, 1H), 7.54-7.48 (m, 3H), 7.45 (dd, J = 9.6,

2.8 Hz, 1H), 7.41 (d, J = 8.8 Hz, 1H), 7.37-7.33 (m, 5H), 7.28-7.26

(m, 2H), 7.20-7.14 (m, 4H), 7.05-6.98 (m, 2H), 6.53 (s, 1H), 5.04 (s,

2H). ¹³C NMR (100 MHz, CDCl₃) δ 159.9 (d, J = 244.0 Hz), 159.9 (d,

J = 243.0 Hz), 154.2 (d, J = 2.9 Hz), 153.5, 152.9, 135.9, 133.9,

133.8, 131.2 (d, J = 7.0 Hz), 131.2, 130.9, 130.9, 130.5 (d, J = 9.1

Hz), 129.9, 129.2 (d, J = 8.8 Hz), 129.0 (d, J = 5.5 Hz), 128.6, 128.6,

128.5, 128.4 (d, J = 5.8 Hz), 128.3, 128.3, 128.0 (d, J = 8.7 Hz),

127.7, 125.6, 125.2, 121.1, 120.9, 120.6, 119.8, 116.9 (d, J = 20.1

Hz), 116.6 (d, J = 19.6 Hz), 114.0, 116.9 (d, J = 20.1 Hz), 116.6 (d, J

= 19.6 Hz), 67.0. ¹⁹F NMR (376 MHz, CDCl₃) δ -116.34, -116.94.

HRMS (ESI) calcd for [M+H] C₃₈H₂₆F₂NO₃, m/z: 582.1875, found:

582.1877.

Benzyl

(7'-methoxy-2'-(naphthalen-2-yloxy)-[1,1'-binaphthalen]-2-yl)carb

amate (5h): white solid, 105.8 mg, 92% yield. H NMR (400 MHz,

1

Benzyl

CDCl₃) δ 8.39 (s, 1H), 7.97 (d, J = 8.8 Hz, 1H), 7.96 (d, J = 8.8 Hz,

1H), 7.89 (d, J = 9.2 Hz, 1H), 7.88 (d, J = 8.4 Hz, 1H), 7.76 (d, J = 7.6

Hz, 1H), 7.65 (d, J = 9.2 Hz, 1H), 7.59 (d, J = 7.6 Hz, 1H), 7.44-7.27

(m, 11H), 7.22 (d, J = 2.4 Hz, 1H), 7.19 (dd, J = 9.2, 2.8 Hz, 1H),

7.01 (dd, J = 8.8, 2.4 Hz, 1H), 6.66 (s, 1H), 6.53 (d, J = 2.8 Hz, 1H),

5.11 (d, J = 12.0 Hz, 1H), 5.07 (d, J = 12.0 Hz, 1H), 3.51 (s, 3H). ¹³C

NMR (100 MHz, CDCl₃) δ 159.0, 154.8, 153.8, 153.7, 136.1, 135.4,

134.3, 134.1, 132.8, 130.7, 130.6, 130.1, 130.0, 129.7, 129.2,

128.6, 128.3, 128.2, 128.1, 127.7, 127.1, 126.5, 126.5, 126.2,

125.6, 124.7, 124.7, 120.3, 120.0, 119.9, 119.7, 117.9, 117.1,

114.1, 103.8, 66.9, 55.2. HRMS (ESI) calcd for [M+H] C₃₉H₃₀NO₄,

m/z: 576.2169, found: 576.2173.

(10-(2-(phenanthren-9-yloxy)naphthalen-1-yl)phenanthren-9-yl)c

arbamate (5l): white solid, 113.5 mg, 88% yield. ¹H NMR (400

MHz, DMSO-d₆) δ 9.33 (s, 1H), 8.88 (d, J = 8.4 Hz, 1H), 8.85 (d, J =

8.4 Hz, 1H), 8.72 (d, J = 8.4 Hz, 1H), 8.68-8.66 (m, 1H), 8.15-8.05

(m, 4H), 7.77-7.67 (m, 3H), 7.63-7.59 (m, 2H), 7.57-7.41 (m, 6H),

7.33-7.26 (m, 7H), 7.09-7.00 (m, 2H), 5.03 (s, 2H). ¹³C NMR (100

MHz, DMSO-d₆) δ 155.4, 152.8, 151.1, 137.6, 133.8, 132.2, 132.1,

131.7, 131.4, 131.0, 130.7, 130.6, 130.6, 130.3, 129.7, 128.7,

128.5, 128.2, 128.0, 127.7, 127.6, 127.5, 127.5, 127.4, 127.4,

127.4, 127.4, 127.4, 127.2, 127.2, 127.4, 126.2, 126.1, 125.3,

125.1, 125.1, 123.6, 123.5, 123.4, 123.2, 123.0, 119.1, 112.3, 65.6.

HRMS (ESI) calcd for [M+H] C₄₆H₃₂NO₃, m/z: 646.2377, found:

646.2371.

Benzyl

(7'-bromo-2'-(naphthalen-2-yloxy)-[1,1'-binaphthalen]-2-yl)carba

mate (5i): white solid, 107.2 mg, 86% yield. H NMR (400 MHz,

CDCl₃) δ 8.52 (s, 1H), 8.04 (d, J = 8.8 Hz, 1H), 7.98 (d, J = 9.2 Hz,

Benzyl

1

(10-(7-methoxy-2-(phenanthren-9-yloxy)naphthalene-1-yl)phenan

thren-9-yl)carbamate (5m): white solid, 121.5 mg, 90% yield. H

1

www.cjc.wiley-vch.de

Chin. J. Chem. 2019, 37, XXX－XXX

Running title

Chin. J. Chem.

NMR (400 MHz, DMSO-d₆) δ 9.38 (s, 1H), 8.88-8.84 (m, 2H), 8.72

(d, J = 8.8 Hz, 1H), 8.69-8.66 (m, 1H), 8.08-8.04 (m, 2H), 7.97 (t, J =

8.4 Hz, 2H), 7.76-7.50 (m, 9H), 7.44-7.41 (m, 2H), 7.26-7.20 (m,

3H), 7.16 (dd, J = 8.8, 2.4 Hz, 1H), 7.07 (d, J = 9.2 Hz, 1H),

7.02-6.94 (m, 2H), 6.75 (s, 1H), 5.13-4.99 (m, 2H), 3.47 (s, 3H). ¹³C

NMR (100 MHz, DMSO-d₆) δ 158.4, 155.7, 153.9, 150.7, 137.5,

135.2, 132.2, 132.1, 131.7, 131.4, 131.0, 130.5, 130.2, 130.2,

130.3, 129.8, 128.7, 128.7, 128.2, 128.1, 128.0, 127.6, 127.6,

127.5, 127.5, 127.4, 127.4, 127.3, 127.2, 126.9, 126.1, 125.8,

125.1, 123.6, 123.6, 123.4, 123.3, 122.9, 121.3, 117.6, 115.7,

113.2, 104.5, 65.7, 55.1. HRMS (ESI) calcd for [M+H] C₄₇H₃₄NO₄,

m/z: 676.2482, found: 676.2480.

mg, 0.22 mmol) and Cs₂CO₃(81.5 mg, 0.25 mmol) were added to

a bottle with a stirring bar. Toluene (2.0 mL) were added and the

reaction mixture was stirred for 48 h at room temperature till 4a

was completely consumed (monitored by TLC). After evaporated

the solvent under reduced pressure, the residue was purified by

flash chromatography eluted with DCM to afford the

corresponding product 5a in 93% yield.

V. Gram-scale synthesis of 3a and the removal of protecting

group.

Figurer 5a: 1a (879 mg, 3.0 mmol) and Na₂CO₃(371 mg, 3.5

mmol) were added to a bottle with a stirring bar. Pre-mixed

solvent (75 mL DCM and 15 mL CF₃CH₂OH) was added and the

reaction mixture was stirred for 15 min. 2a (1.55 g, 3.3 mmol) was

added in batches and then the reaction mixture was stirred at

room temperature for 72 h. After 1a was completely consumed

(monitored by TLC), the solvent was evaporated under reduced

pressure. The residue was purified by flash chromatography

eluted with DCM to afford the corresponding product 3a (1.19 g,

95% yield).

A mixture of 3a (83.8 mg, 0.2 mmol), 5 mL 40% KOH aqueous

solution, and 6 mL EtOH was refluxed for 12 h. The reaction was

quenched by HCl (2 M) and then saturated sodium bicarbonate

solution was added to neutralize the solution. The aqueous layer

was extracted with DCM. The combined organic layers were dried

over Na₂SO₄, filtered, and concentrated under reduced pressure.

The residue was purified by flash chromatography to afford

(Rac)-6a (54.2 mg, 95% yield).

A mixture of 3a (83.8 mg, 0.2 mmol), AcOH (3.0 mL) and con.

HCl (1.0 mmol) was refluxed for 12 h. Sodium bicarbonate

solution was added to neutralize the solution. The aqueous layer

was extracted with DCM. The combined organic layers were dried

over Na₂SO₄, filtered, and concentrated under reduced pressure.

The residue was purified by flash chromatography to afford

(Rac)-6a (51.3 mg, 90% yield).

Pd/C (10 mg) was added to a solution of 3a (83.8 mg, 0.2

mmol) in MeOH/CHCl₃(1/1, 5.0 mL). The resulting mixture was

stirred at room temperature under H₂atmosphere. When TLC

indicated the reaction was completed, the solution was carefully

poured into another bottle. Then the obtained crude material was

purified by flash chromatography to afford (Rac)-6a (51.1 mg, 90%

yield).

III. Control experiments

a) No change was observed in ¹H NMR spectrum after the

addition of equivalent Na₂CO₃, indicating that the reaction did not

undergo via a benzyne process.

b) 1a (29.3 mg, 0.10 mmol), 2a (49.1 mg, 0.11 mmol), TEMPO

(15.6 mg, 0.10 mmol) and Na₂CO₃(12.7 mg, 0.12 mmol) were

added to a bottle with a stirring bar. Pre-mixed solvent (1.67 mL

DCM and 0.33 mL CF₃CH₂OH) was added and the reaction mixture

was stirred for 24 h at room temperature till 1a was completely

consumed (monitored by TLC). After evaporated the solvent

under reduced pressure, the residue was purified by flash

chromatography eluted with DCM to afford the corresponding

product 3a in 86% yield. The result revealed that a radical course

could be ruled out.

c) 3a (41.9 mg, 0.10 mmol), 2a (49.1 mg, 0.11 mmol) and

Na₂CO₃(12.7 mg, 0.12 mmol) or Cs₂CO₃(39.1 mg, 0.12 mmol)

were added to a bottle with a stirring bar. DCM (2.0 mL) or

toluene (2.0 mL) was added and the reaction mixture was stirred

for 24 h at room temperature till 3a was completely consumed

(monitored by TLC). After evaporated the solvent under reduced

pressure, the residue was purified by flash chromatography

eluted with DCM to afford the corresponding product 5a

quantitatively.

IV. Investigations of diarylchloronium and diarylbrominium salts.

Figurer 4a: 1a (29.3 mg, 0.10 mmol), 2 (0.11 mmol) and

Na₂CO₃(12.7 mg, 0.12 mmol) were added to a bottle with a

stirring bar. THF (2.0 mL) were added and the reaction mixture

was stirred for 48 h at room temperature till 1a was completely

consumed (monitored by TLC). After evaporated the solvent

under reduced pressure, the residue was purified by flash

chromatography eluted with DCM to afford the corresponding

product 3a.

Figurer 4b, Conditions A: 4a (29.3 mg, 0.10 mmol), 2r (113.2

mg, 0.10 mmol) were added to a bottle with a stirring bar. DCM

(2.0 mL) was added and stirred for 5 minutes. DIPEA (14.2 mg,

0.11 mmol) was added to the reaction mixture and stirred for 48

VI. Diastereoselective [3,3]-sigmatropic rearrangement.

Figurer 5b: 1p (68.2 mg, 0.20 mmol), 2a (107.0 mg, 0.24 mmol)

and Na₂CO₃(26.5 mg, 0.25 mmol) were added to a bottle with a

stirring bar. Pre-mixed solvent (4 mL DCM and 1 mL CF₃CH₂OH)

was added and the reaction mixture was stirred for 12 h at room

temperature till 1p was completely consumed (monitored by TLC).

After evaporated the solvent, the residue was purified by flash

chromatography eluted with PE/THF to afford the corresponding

products 3aj and 3ak.

A mixture of 3aj or 3ak (35 mg, 0.075 mmol), 40% KOH (2 mL)

aqueous solution, and 4 mL EtOH was refluxed for 12 h. The

reaction was quenched by HCl (2 M) and then saturated sodium

bicarbonate solution was added to neutralize the reaction

h

at room temperature till 4a was completely consumed

(monitored by TLC). After evaporated the solvent under reduced

pressure, the residue was purified by flash chromatography

eluted with DCM to afford the corresponding product 3a in 25%

yield and 5a in 36% yield.

Figurer 4b, Conditions B: 4a (29.3 mg, 0.10 mmol), 2r (249.0

Chin. J. Chem. 2019, 37, XXX－XXX

www.cjc.wiley-vch.de

Zhang et al.

Report

solution. The aqueous layer was extracted with DCM. The

combined organic layers were dried over Na₂SO₄, filtered, and

concentrated under reduced pressure. The residue was purified

by flash chromatography to afford (S)-6a or (R)-6a.

It is necessary to stir at room temperature for another 36 h. The

crude mixture was directly purified by silica gel column

chromatography with hexane/EtOAc as eluent to afford the

esterification product and the recovered starting material in

optically active form.

(1R,2S,5R)-2-isopropyl-5-methylcyclohexyl

((S)-2'-hydroxy-[1,1'-binaphthalen]-2-yl)carbamate (3aj): white

solid, 38.4 mg, 41% yield. H NMR (400 MHz, CDCl₃) δ 8.43 (d, J =

(S)-benzyl (2'-hydroxy-[1,1'-binaphthalen]-2-yl)carbamate (3a):

white solid, 25.5 mg, 32% yield, 91% ee. HPLC analysis: DAICEL

CHIRALCEL ID, hexane/isopropanol = 85/15, 1.0 mL/min, λ = 254

nm, t_R(minor) = 14.4 min, t_R(major) = 19.0 min, ee = 91%.

(R)-2'-(((benzyloxy)carbonyl)amino)-[1,1'-binaphthalen]-2-yl

3-methylbutanoate (9a): white solid, 41.1 mg, 43% yield, 56% ee.

¹H NMR (400 MHz, CDCl₃) δ 8.35 (d, J = 8.4 Hz, 1H), 8.10 (d, J = 9.2

Hz, 1H), 8.04 (d, J = 8.8 Hz, 1H), 8.01 (d, J = 8.4 Hz, 1H), 7.93 (d, J =

8.4 Hz, 1H), 7.56-7.52 (m, 1H), 7.46-7.42 (m, 2H), 7.36-7.23 (m,

8H), 7.15 (d, J = 8.4 Hz, 1H), 6.73 (s, 1H), 5.20-5.04 (m, 2H),

2.08-1.96 (m, 2H), 1.70-1.61 (m, 1H), 0.60-0.57 (m, 6H). ¹³C NMR

(100 MHz, CDCl₃) δ 172.0, 153.9, 147.5, 136.3, 134.8, 133.1, 132.7,

132.2, 130.7, 130.7,129.4, 128.5, 128.4, 128.0, 127.9, 127.9, 127.5,

126.7, 126.2, 125.5, 125.4, 125.0, 124.5, 121.9, 121.1, 120.5, 66.7,

42.8, 25.4, 21.9, 21.9. HRMS (ESI) calcd for [M+H] C₃₃H₃₀NO₄, m/z:

504.2169, found: 504.2163. HPLC analysis: DAICEL CHIRALCEL ID,

hexane/isopropanol = 85/15, 1.0 mL/min, λ = 254 nm, t_R(minor) =

7.9 min, t_R(major) = 16.7 min, ee = 56%.

1

9.2 Hz, 1H), 8.07 (d, J = 9.2 Hz, 1H), 8.00 (d, J = 8.8 Hz, 1H), 7.94 (d,

J = 8.0 Hz, 1H), 7.93 (d, J = 8.0 Hz, 1H), 7.45 (t, J = 7.6 Hz, 1H),

7.41-7.38 (m, 2H), 7.33-7.28 (m, 2H), 7.15 (d, J = 8.4 Hz, 1H), 7.05

(d, J = 8.4 Hz, 1H), 6.33 (s, 1H), 5.20 (s, 1H), 4.61 (td, J = 10.8, 4.4

Hz, 1H), 2.01-1.95 (m, 1H), 1.81-1.74 (m, 1H), 1.71-1.61 (m, 2H),

1.54-1.41 (m, 1H), 1.27-1.19 (m, 1H), 1.10-0.89 (m, 3H), 0.89 (d, J

= 6.8 Hz, 3H), 0.86 (d, J = 6.8 Hz, 3H), 0.77 (d, J = 6.8 Hz, 3H). ¹³C

NMR (100 MHz, CDCl₃) δ 154.0, 152.1, 136.1, 133.3, 133.0, 131.1,

130.9, 130.3, 129.3, 128.4, 128.3, 127.3, 127.3, 125.2, 125.2,

124.3, 123.9, 120.6, 117.9, 117.4, 112.9, 75.6, 47.0, 41.1, 34.2,

31.4, 26.4, 23.7, 22.0, 20.6, 16.7. HRMS (ESI) calcd for [M+H]

C₃₁H₃₄NO₃, m/z: 468.2533, found: 468.2530.

(1R,2S,5R)-2-isopropyl-5-methylcyclohexyl

((R)-2'-hydroxy-[1,1'-binaphthalen]-2-yl)carbamate (3ak): white

1

solid, 46.7 mg, 50% yield. H NMR (400 MHz, CDCl₃) δ 8.47 (d, J =

9.2 Hz, 1H), 8.07 (d, J = 9.2 Hz, 1H), 8.00 (d, J = 8.8 Hz, 1H), 7.93 (t,

J = 8.0 Hz, 2H), 7.45 (t, J = 7.2 Hz, 1H), 7.42-7.27 (m, 4H), 7.19 (d, J

= 8.4 Hz, 1H), 7.08 (d, J = 8.4 Hz, 1H), 6.32 (s, 1H), 5.11 (s, 1H),

4.57 (td, J = 10.8, 4.4 Hz, 1H), 2.05-1.99 (m, 1H), 1.67-1.57 (m, 2H),

1.53-1.42 (m, 2H), 1.19-1.13 (m, 1H), 1.06-0.76 (m, 3H), 0.90 (d, J

= 6.8 Hz, 3H), 0.72 (d, J = 6.8 Hz, 3H), 0.65 (d, J = 6.8 Hz, 3H). ¹³C

NMR (100 MHz, CDCl₃) δ 153.8, 152.0, 136.2, 133.1, 132.8, 131.1,

130.8, 130.2, 129.4, 128.4, 128.3, 127.4, 127.3, 125.2, 125.0,

124.1, 123.9, 120.3, 117.9, 116.9, 112.9, 75.4, 47.0, 41.1, 34.2,

31.4, 26.1, 23.6, 22.0, 20.5, 16.5. HRMS (ESI) calcd for [M+H]

C₃₁H₃₄NO₃, m/z: 468.2533, found: 468.2535.

Supporting Information

The supporting information for this article is available on the

WWW under https://doi.org/10.1002/cjoc.2018xxxxx.

Acknowledgement

We are grateful for financial support from the National

Natural Science Foundation of China (Nos. 21772081, 21825105,

21801117), Guangdong Provincial Key Laboratory of Catalysis (No.

(S)-2'-amino-[1,1'-binaphthalen]-2-ol (6a): white solid, 20.3

1

2020B121201002),

(2019BT02Y335),

Guangdong

Shenzhen

Innovative

Special

Program

Funds

mg, Yield 95%, 99% ee. H NMR (400 MHz, DMSO-d₆) δ 9.40 (s,

1H), 7.91 (d, J = 8.8 Hz, 1H), 7.88 (d, J = 8.0 Hz, 1H), 7.77-7.74 (m,

2H), 7.42 (d, J = 8.8 Hz, 1H), 7.22-7.27 (m, 2H), 7.21-7.17 (m, 1H),

7.12-7.06 (m, 2H), 7.00 (d, J = 8.4 Hz, 1H), 6.80-6.83 (m, 1H), 4.57

(s, 2H). ¹³C NMR (100 MHz, DMSO-d₆) δ 153.8, 144.4, 134.5, 134.2,

129.7, 129.0, 128.7, 128.6, 128.3, 127.6, 126.7, 126.2, 124.6,

124.0, 123.1, 121.3, 119.3, 119.0, 115.5, 111.9. HPLC analysis:

(S)-6a: DAICEL CHIRALCEL OJ-H, hexane/isopropanol = 80/20, 1.0

mL/min, λ = 254 nm, t_R(minor) = 19.1 min, t_R(major) = 24.7 min,

ee = 99%. (R)-6a: DAICEL CHIRALCEL OJ-H, hexane/isopropanol =

80/20, 1.0 mL/min, λ = 254 nm, t_R(major) = 18.6 min, t_R(minor) =

24.8 min, ee = 99%.

(JCYJ20180305123508258), and Shenzhen Nobel Prize Scientists

Laboratory Project (C17213101).

References

(a) Kočovský, P.; Vyskočil, Š.; Smrčina, M. Non-Symmetrically Substituted

1,1′-Binaphthyls in Enantioselective Catalysis. Chem. Rev. 2003, 103,

3213–3245. (b) Ding, K.; Li, X.; Ji, B.; Guo, H.; Kitamura, M. Ten Years of

Research on NOBIN Chemistry. Curr. Org. Syn. 2005, 2, 499–545. (c) Ding,

K.; Guo, H.; Li, X.; Yuan, Y.; Wang, Y. Synthesis of NOBIN Derivatives for

Asymmetric Catalysis. Top. Catal. 2005, 35, 105–116. (d) Wang, Y.-B.; Tan,

B. Construction of Axially Chiral Compounds via Asymmetric

Organocatalysis. Acc. Chem. Res. 2018, 51, 534–547. (e) Carreira, E. M.;

Lee, W.; Singer, R. A. Catalytic, Enantioselective Acetone Aldol Additions

with 2-Methoxypropene. J. Am. Chem. Soc. 1995, 117, 3649–3650. (f)

Singer, R. A.; Carreira, E. M. Catalytic, Enantioselective Dienolate

Additions to Aldehydes: Preparation of Optically Active Acetoacetate

Aldol Adducts. J. Am. Chem. Soc. 1995, 117, 12360–12361. (g) Van

VII. Chiral NHC-catalyzed kinetic resolution.

Figurer 5c: Under argon atmosphere, 1a (55.7 mg, 0.19 mmol),

2r (237.7 mg, 0.21 mmol) and 4Å MS (50 mg) were added to a

tube with a stirring bar. Anhydrous THF (0.8 mL) was added and

stirred for 5 minutes. Anhydrous DIPEA (28.4 mg, 0.22 mmol) was

added to the reaction mixture and stirred for 48 h at room

temperature till 1a was completely consumed (monitored by TLC).

Subsequently, aldehyde 8 (20.6 mg, 0.10 mmol), and additional

DIPEA (19.4 mg, 0.15 mmol) were added. The mixture was stirred

for 1 min before triazolium salt 7 (8.5 mg, 0.019 mmol) was added.

Veldhuizen, J. J.; Garber, S. B.; Kingsbury, J. S.; Hoveyda, A. H.

A

Recyclable Chiral Ru Catalyst for Enantioselective Olefin Metathesis.

Efficient Catalytic Asymmetric Ring-Opening/Cross Metathesis in Air. J.

www.cjc.wiley-vch.de

Chin. J. Chem. 2019, 37, XXX－XXX

Running title

Chin. J. Chem.

Am. Chem. Soc. 2002, 124, 4954–4955. (h) Yan, Y.; Zhang, X. A Hybrid

Calculations. J. Am. Chem. Soc. 2013, 135, 7086–7089. (c) De, C. K.;

Pesciaioli, F.; List, B. Catalytic Asymmetric Benzidine Rearrangement.

Angew. Chem. Int. Ed. 2013, 52, 9293–9295. (d) Li, G.-Q.; Gao, H.; Keene,

C.; Devonas, M.; Ess, D. H.; Kürti, L. Organocatalytic Aryl-Aryl Bond

Formation: An Atroposelective [3,3]-Rearrangement Approach to BINAM

Derivatives. J. Am. Chem. Soc. 2013, 135, 7414–7417. (e) Yanagi, T.;

Otsuka, S.; Kasuga, Y.; Fujimoto, K.; Murakami, K.; Nogi, K.; Yorimitsu, H.;

Osuka, A. Metal-free Approach to Biaryls from Phenols and Aryl

Sulfoxides by Temporarily Sulfur-Tethered Regioselective C−H/C−H

Coupling. J. Am. Chem. Soc. 2016, 138, 14582–14585. (f) Shrives, H. J.;

Fernández-Salas, J. A.; Hedtke, C.; Pulis, A. P.; Procter, D. J. Regioselective

Synthesis of C3 Alkylated and Arylated Benzothiophenes. Nat. Commun.

2017, 8, 14801–14808. (g) Hori, M.; Guo, J.-D.; Yanagi, T.; Nogi, K.;

Sasamori, T.; Yorimitsu, H. Sigmatropic Rearrangements of

Hypervalent-Iodine-Tethered Intermediates for the Synthesis of Biaryls.

Angew. Chem. Int. Ed. 2018, 57, 4663–4667. (h) Guo, L.; Liu, F.; Wang, L.;

Yuan, H.; Feng, L.; Kürti, L.; Gao, H. Cascade Approach to Highly

Phosphorus Ligand for Highly Enantioselective Asymmetric

Hydroformylation. J. Am. Chem. Soc. 2006, 128, 7198–7202. (i) Uraguchi,

D.; Kinoshita, N.; Ooi T. Catalytic Asymmetric Protonation of α-Amino

Acid-Derived

Ketene

Disilyl

Acetals

Using

P-Spiro

Diaminodioxaphosphonium Barfates as Chiral Proton. J. Am. Chem. Soc.

2010, 132, 12240–12242. (j) Alegre-Requena, J. V.; Marqués-López, E.;

Herrera, R. P. “Push−Pull π+/π−” (PPππ) Systems in Catalysis. ACS Catal.

2017, 7, 6430–6439. (k) Vallavoju, N.; Selvakumar, S.; Jockusch, S.; Sibi, M.

P.; Sivaguru, J. Enantioselective Organo-Photocatalysis Mediated by

Atropisomeric Thiourea Derivatives. Angew. Chem. Int. Ed. 2014, 53,

5604–5608. (l) Lipshutz, B. H.; Buzard, D. J.; Olsson, C.; Noson, K. A

Modular Route to Nonracemic Cyclo-NOBINs. Preparation of the Parent

Ligand for Homo- and Heterogeneous Catalysis. Tetrahedron 2004, 60,

4443–4449.

(a) Pu, L. 1,1'-Binaphthyl Dimers, Oligomers, and Polymers: Molecular

Recognition, Asymmetric Catalysis, and New Materials. Chem. Rev. 1998,

98, 2405–2494. (b) Lynch, J. G.; Jaycox, G. D. Stimuli-Responsive Polymers.

10. Photo-Regulation of Optical Rotations in Azobenzene Modified

Poly(ester-amide)s Containing Highly Structured, Atropisomeric Backbone

Geometries. Polymer 2014, 55, 3564–3572. (c) Hassan, F.; Sassa, T.;

Hirose, T.; Ito, Y.; Kawamoto, M. Light-Driven Molecular Switching of

Atropisomeric Polymers Containing Azo-Binaphthyl Groups in Their Side

Chains. Polym. J. 2018, 50, 455–465. (d) Lakshmipriya, A.; Chaudhari, S. R.;

Suryaprakash, N. p-TsOH Promotes 2'-Amino-[1,1'-binaphthalene]-2-ol as

A Chiral Solvating Agent. New J. Chem. 2016, 40, 8118–8122.

Functionalized Biaryls by

a Nucleophilic Aromatic Substitution with

Arylhydroxylamines. Org. Lett. 2019, 21, 2894–2898.

(a) Deprez, N. R.; Sanford, M. S. Reactions of Hypervalent Iodine Reagents

with Palladium: Mechanisms and Applications in Organic Synthesis. Inorg.

Chem. 2007, 46, 1924–1935. (b) Merritt, E. A.; Olofsson B. Diaryliodonium

Salts: A Journey from Obscurity to Fame. Angew. Chem. Int. Ed. 2009, 48,

9052–9070. (c) Olofsson; B. Arylation with Diaryliodonium Salts. Top. Curr.

Chem. 2016, 373, 135–166. (d) Aradi, K.; Tóth, B. L.; Tolnai, G. L.; Novák, Z.

Diaryliodonium Salts in Organic Syntheses: A Useful Compound Class for

Novel Arylation Strategies. Synlett 2016, 27, 1456–1485. (e) Stuart, D. R.

Aryl Transfer Selectivity in Metal-Free Reactions of Unsymmetrical

Diaryliodonium Salts. Chem. Eur. J. 2017, 23, 15852–15863.

(a)

Singer,

R.

A.;

Buchwald,

S.

L.

and

Preparation

of

2-Amino-2′-hydroxy-1,1'-binaphthyl

N-arylated

2-Amino-1,1'-binaphthyl Derivatives via Palladium-Catalyzed Amination.

Tetrahedron Lett. 1999, 40, 1095–1098. (b) Patel, D. C.; Breitbach, Z. S.;

Woods, R. M.; Lim, Y.; Wang, A.; Foss, F. W. J.; Armstrong, D. W. Gram

Scale Conversion of R-BINAM to R-NOBIN. J. Org. Chem. 2016, 81, 1295–

1299. (c) Chang, X.; Zhang, Q.; Guo, C. Switchable Smiles Rearrangement

for Enantioselective O-Aryl Amination. Org. Lett. 2019, 21, 4915–4918. (d)

Smrčina, M.; Lorenc, M.; Hanuš, V.; Kočovský, P. A Facile Synthesis of

2-Amino-2'-hydroxy-1,1'-binaphthyl and 2,2'-Diamino-1,1'-binaphthyl by

Oxidative Coupling Using Copper(II) Chloride. Synlett l991, 1991, 231–232.

(e) Smčrina, M.; Vyskočil, Š.; Máca, B.; Polášek, M.; Claxton, T. A.; Abbott,

A. P.; Kočovský, P. Selective Cross-Coupling of 2-Naphthol and

2-Naphthylamine Derivatives. A Facile Synthesis of 2,2',3-Trisubstituted

and 2,2',3,3'-Tetrasubstituted-1,1'-Binaphthyls. J. Org. Chem. 1994, 59,

2156–2163. (f) Ding, K.; Xu, Q.; Wang, Y.; Liu, J.; Yu, Z.; Du, B.; Wu, Y.;

Koshima, H.; Matsuura, T. Novel Two-Phase Oxidative Cross-Coupling of

The Two-Component Molecular Crystal of 2-Naphthol and

2-Naphthylamine. Chem. Commun. 1997, 693–694. (g) Singer, R. A.; Brock,

(a) Beringer, F. M.; Brierley, A.; Drexler, M.; Gindler, E. M.; Lumpkin, C. C.

Diaryliodonium Salts. II. The Phenylation of Organic and Inorganic Bases. J.

Am. Chem. Soc. 1953, 75, 2708–2712. (b) Ozanne-Beaudenon, A.;

Quideau,

S.

Regioselective

Hypervalent-Iodine(III)-Mediated

Dearomatizing Phenylation of Phenols through Direct Ligand Coupling.

Angew. Chem. Int. Ed. 2005, 44, 7065–7069. (c) Ackermann, L.; Dell’Acqua,

M.; Fenner, S.; Vicente, R.; Sandmann, R. Metal-Free Direct Arylations of

Indoles and Pyrroles with Diaryliodonium Salts. Org. Lett. 2011, 13, 2358–

2360. (d) Wen, J.; Zhang, R.-Y.; Chen, S.-Y.; Zhang, J.; Yu, X.-Q. Direct

Arylation of Arene and N-Heteroarenes with Diaryliodonium Salts without

the Use of Transition Metal Catalyst. J. Org. Chem. 2012, 77, 766–771. (e)

Castro, S.; Fernández, J. J.; Vicente, R.; Fañanás, F. J.; Rodríguez, F. Base-

and Metal-Free C–H Direct Arylations of Naphthalene and Other

Unbiased Arenes with Diaryliodonium Salts. Chem. Commun. 2012, 48,

9089–9091. (f) Ghosh, M. K.; Rzymkowski, J.; Kalek, M.

Transition-Metal-Free Aryl-Aryl Cross-Coupling: C-H Arylation of

2-Naphthols with Diaryliodonium Salts. Chem. Eur. J. 2019, 25, 9619–

9623.

J. R.; Carreira, E. M. Synthesis of

a Tridentate Ligand for Use in

Ti^IV-Catalyzed Acetate Aldol Addition Reactions. Helv. Chim. Acta 2003, 86,

1040—1044. (h) Forkosh, H.; Vershinin, V.; Reiss, H.; Pappo, D.

(a) Chen, Y.-H.; Cheng, D.-J.; Zhang, J.; Wang, Y.; Liu, X.-Y.; Tan, B.

Atroposelective Synthesis of Axially Chiral Biaryldiols via Organocatalytic

Arylation of 2-Naphthols. J. Am. Chem. Soc. 2015, 137, 15062–15065. (b)

Chen, Y.-H.; Qi, L.-W.; Fang, F.; Tan, B. Organocatalytic Atroposelective

Arylation of 2-Naphthylamines as a Practical Approach to Axially Chiral

Biaryl Amino Alcohols. Angew. Chem. Int. Ed. 2017, 56, 16308–16312. (c)

Qi, L.-W.; Mao, J.-H.; Zhang, J.; Tan, B. Organocatalytic Asymmetric

Arylation of Indoles Enabled by Azo Groups. Nat. Chem. 2018, 10, 58–64.

(d) Zhu, S.; Chen, Y.-H.; Wang, Y.-B.; Yu, P.; Li, S.; Xiang, S.-H.; Wang, J.-Q.;

Stereoselective

Synthesis

of

Optically

Pure

2-Amino-2'-hydroxy-1,1'-binaphthyls. Org. Lett. 2018, 20, 2459–2463.

(a) Sheradsky, T.; Avramovici-Grisaru, S. Hydrolytic Cleavages of

7-Nitro-2-phenyl-1,2-benzisoxazol-3-one. Evidence for the Occurrence of

A

Benzidine-like Rearrangement of N,O-diphenylhydroxylamines.

Heterocycl. Chem. 1980, 17, 189–190. (b) Gao, H.; Ess, D. H.; Yousufuddin,

M.; Kürti, L. Transition-Metal-Free Direct Arylation: Synthesis of

Halogenated 2-Amino-2'-hydroxy-1,1'-biaryls and Mechanism by DFT

Chin. J. Chem. 2019, 37, XXX－XXX

www.cjc.wiley-vch.de

Zhang et al.

Report

Xiao, J.; Tan, B. Organocatalytic Atroposelective Construction of Axially

Mechanistic Insights. Chem. Eur. J. 2017, 23, 13249–13258.

Chiral Arylquinones. Nat. Commun. 2019, 10, 4268–4278. (e) Yan, S.; Xia,

W.; Li, S.; Song, Q.; Xiang, S.-H.; Tan, B. Michael Reaction Inspired

Atroposelective Construction of Axially Chiral Biaryls. J. Am. Chem. Soc.

2020, 142, 7322–7327.

During the evaluation of the manuscript in Angewandte Chieme, a similar

work was published. Yuan, H.; Du, Y.; Liu, F.; Guo, L.; Sun, Q.; Feng, L.;

Gao, H. Tandem approach to NOBIN analogues from arylhydroxylamines

and diaryliodonium salts via [3,3]-sigmatropic rearrangement. Chem.

Commun. 2020, 56, DOI: 10.1039/d0cc02919j.

Nakajima, M.; Miyamoto, K.; Hirano, K.; Uchiyama, M. Diaryl-λ³-chloranes:

Versatile Synthesis and Unique Reactivity as Aryl Cation Equivalent. J. Am.

Chem. Soc. 2019, 141, 6499–6503.

(a) Qi, L.-W.; Li, S.; Xiang, S.-H.; Wang, J.; Tan, B. Asymmetric Construction

of Atropisomeric Biaryls via A Redox Neutral Cross-coupling Strategy. Nat.

Catal. 2019, 2, 314–323. (b) Ding, W.-Y.; Yu, P.; An, Q.-J.; Bay, K. L.; Xiang,

S.-H.; Li, S.; Chen, Y.; Houk, K. N.; Tan, B. DFT-Guided Phosphoric

Acid-Catalyzed

Atroposelective

Arene

Functionalization

of

Nitrosonaphthalene. Chem 2020, 10.1016/j.chempr.2020.06.001.

(a) Kita, Y.; Dohi, T. Pioneering Metal-Free Oxidative Coupling Strategy of

Aromatic Compounds Using Hypervalent Iodine Reagents. Chem. Rec.

2015, 15, 886–906. (b) Ochiai, M. Reactivities, Properties and Structures.

Top. Curr. Chem. 2003, 224, 5–68. (c) de Magalhães, H. P.; Lüthi, H. P.;

Togni, A. Reductive Eliminations from λ³-Iodanes: Understanding

Selectivity and the Crucial Role of the Hypervalent Bond. Org. Lett. 2012,

14, 3830–3833. (d) Norrby, P.-O.; Petersen, T. B.; Bielawski, M.; Olofsson,

B. α-Arylation by Rearrangement: On the Reaction of Enolates with

Diaryliodonium Salts. Chem. Eur. J. 2010, 16, 8251–8254.

Lu, S.; Poh, S. B.; Zhao, Y. Kinetic Resolution of 1,1'-Biaryl-2,2'-Diols and

Amino Alcohols through NHC-Catalyzed Atroposelective Acylation. Angew.

Chem. Int. Ed. 2014, 53, 11041–11045.

(The following will be filled in by the editorial staff)

Manuscript received: XXXX, 2019

Manuscript revised: XXXX, 2019

Manuscript accepted: XXXX, 2019

Accepted manuscript online: XXXX, 2019

Version of record online: XXXX, 2019

Stridfeldt, E.; Lindstedt, E.; Reitti, M.; Blid, J.; Norrby, P.-O.; Olofsson, B.

Competing Pathways in O-Arylations with Diaryliodonium Salts:

www.cjc.wiley-vch.de

Chin. J. Chem. 2019, 37, XXX－XXX

Running title

Chin. J. Chem.

Entry for the Table of Contents

OH

N

Page No.

Direct Construction of NOBINs via Domino

Arylation and Sigmatropic Rearrangement

Reactions

[3,3]-

rearrangement

Y

X

Ar¹

Ar²

R

NH₂

OH

N

O

Arylation

=

X

Br, Cl

I,

H

N

O

and

Transition metal-free

Versatile

nucleophiles

Diversified NOBINs

reagents

arylation

Complete regioselectivity

Privileged NOBIN frameworks were constructed through

a

novel domino arylation of

naphthylhydroxylamines with diarylhalonium salts and sigmatropic rearrangement in a transition

metal-free fashion. Optically active product was accessible by chiral NHC-catalyzed kinetic

resolution in one pot or diastereoselective [3,3]-rearrangement. Remarkably, diarylchloronium and

diarylbrominium salts have been employed as arylation reagents for the first time in assembling

such representative biaryl frameworks.

Ji-Wei Zhang, Liang-Wen Qi, Shaoyu Li,*

Shao-Hua Xiang, Bin Tan*

Chin. J. Chem. 2019, 37, XXX－XXX

www.cjc.wiley-vch.de

Article Doi

Direct Construction of NOBINs via Domino Arylation and Sigmatropic Rearrangement Reactions

DOI: 10.1002/cjoc.202000358

Source and publish data:

Authors:

Article abstract of DOI:10.1002/cjoc.202000358

Full text of DOI:10.1002/cjoc.202000358

Products guided by the article

R&D Labs maybe for 13202-18-1

Relevant to this article

Hot Product