Synthesis of 1,2-naphthalenediol derivatives by Rh-catalyzed intermolecular O[sbnd]H insertion reaction of 1,2-diazonaphthoquinones with water and alcohols

Article abstract of DOI:10.1016/j.tetlet.2017.07.084

Rh(II)-catalyzed O[sbnd]H insertion reaction of diazonaphthoquinones with water or alocohols proceeded to yield 1,2-naphthalenediol derivatives.

Full text of DOI:10.1016/j.tetlet.2017.07.084

Accepted Manuscript
Synthesis of 1,2-Naphthalenediol Derivatives by Rh-catalyzed Intermolecular
O-H Insertion Reaction of 1,2-Diazonaphthoquinones with Water and Alcohols
Mitsuru Kitamura, Kota Otsuka, Shuhei Takahashi, Tatsuo Okauchi
PII:
S0040-4039(17)30948-6
DOI:
http://dx.doi.org/10.1016/j.tetlet.2017.07.084
TETL 49166
Reference:
Tetrahedron Letters
To appear in:
Received Date:
Revised Date:
Accepted Date:
5 June 2017
19 July 2017
25 July 2017
Please cite this article as: Kitamura, M., Otsuka, K., Takahashi, S., Okauchi, T., Synthesis of 1,2-Naphthalenediol
Derivatives by Rh-catalyzed Intermolecular O-H Insertion Reaction of 1,2-Diazonaphthoquinones with Water and
Alcohols, Tetrahedron Letters (2017), doi: http://dx.doi.org/10.1016/j.tetlet.2017.07.084
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Synthesis of 1,2-Naphthalenediol Derivatives
by Rh-catalyzed Intermolecular O-H
Insertion Reaction of 1,2-
Diazonaphthoquinones with Water and
Alcohols
Mitsuru Kitamura,* Kota Otsuka, Shuhei Takahashi, Tatsuo Okauchi

1
Tetrahedron Letters
journal homepage: www.els evier.com
Synthesis of 1,2-Naphthalenediol Derivatives by Rh-catalyzed Intermolecular O-H
Insertion Reaction of 1,2-Diazonaphthoquinones with Water and Alcohols
Mitsuru Kitamura,* Kota Otsuka, Shuhei Takahashi, and Tatsuo Okauchi
Department of Applied Chemistry, Graduate School of Engineering, Kyushu Institute of Technology, 1-1 Sensuicho, Tobata, Kitakyushu, 804-8550 Japan
ARTICLE INFO
ABSTRACT
Article history:
Received
Rh(II)-catalyzed O-H insertion reaction of diazonaphthoquinones with water or alocohols
proceeded to yield 1,2-naphthalenediol derivatives.
Received in revised form
Accepted
Available online
2009 Elsevier Ltd. All rights reserved.
Keywords:
diazonaphthoquinones
naphthalenediol
O-H insertion
rhodium
Similar to catechol derivatives, 1,2-naphthalenediols are
attractive possible aromatic functional materials (or their building
blocks), such as solar cells, metal ligands, and anti-oxidants.1
However, there are only a few reports regarding the synthesis of
1,2-naphthalenediols.2
Recently, we developed an easy method of synthesis of
diazonaphthoquinones (DNQ) from corresponding naphthols by
diazo-transfer reaction using azidoimidazolinium salt (ADMC)
(Scheme 1).3,4 By the reaction of 1-naphthol or 2-naphthol with
ADMC, 2-diazotized DNQ 1 or 1-diazotized DNQ 2 was
selectively obtained, respectively.
water in solvent (Scheme 2).9 Inspired by the result, we
considered that 1,2-naphthalenediols could be synthesized by the
Rh(II)-catalyzed intermolecular O–H insertion reaction between
1,2-DNQs and water and started to examine the consideration.10
Furthermore, we examined the O–H insertion reaction with
alcohol. In this letter, we report the results in detail.
Scheme 2. Rh-catalyzed reaction of 3-
propyloxycarbonyldiazonaphthoquinone 1a.
Scheme 1. Synthesis of diazonaphthoquinones by the reaction of
naphthol with azidoimidazolinium salt (ADMC).
As shown in Table 1, naphthalenediols 4 were obtained by the
Rh(II)-catalyzed reaction of DNQs in the presence of water.
When a mixture of DNQ 1a in benzene was heated at 60 °C for 7
h in the presence of 3 mol% Rh2(OAc)4 and 1 equiv. of water,
naphthalenediol 4a was obtained quantitatively (run 1). Various
3-carbonylgroup substituted DNQs, such as ester 1a–e and
aldehyde 1f gave corresponding O–H insertion products 4a–f in
good yields. When 3-unsubstituted 1h and 3-methyl-substituted
1i were employed for the reaction, DNQs were consumed within
1 hour. However, expected O–H insertion products were not
obtained at all. 3-Alkoxycarbonyl DNQs 1 were found to be
DNQs have been used exclusively as photoresists such as
novolak-DNQ resist,5 and we are addressing the development of
poly-substituted aromatic compounds from the DNQs.6,7
During the course our study of Rh(II)-catalyzed reaction8 of
propyloxycaroonyl-2-diazotized DNQ 1a expecting the
preparation of 3 by intramolecular C–H insertion reaction, we
found the formation of naphthalenediol 4a, which would be
formed by the intermolecular O–H insertion of contaminated

2
Tetrahedron Letters
more stable than 3-unsubstituted and 3-alkyl-substituted DNQs
Next, we examined the Rh-catalyzed reaction with alcohol
(Table 2). In the reaction mixture, molecular sieve 4A was added
to avoid the formation of diol formed by the reaction with
contaminated water.
In runs 1–10 the results of the reaction of 3-methoxycarbonyl
DNQ 1b and alcohols are shown. Various alcohols, such as
methanol, benzyl alcohol, tert-butyl alcohol, phenol, and glycolic
acid ester reacted with 1b to afford corresponding
naphthalenediol derivatives 5 in good to high yields (runs 1–7).
In the reaction with allylic alcohol, the reaction mixture became
complex, but the expected diol derivative 5h was isolated in 40%
yield (run 8). Interestingly, tricyclic compound 6a was obtained
primarily in the reaction with propargyl alcohol (run 9).
like 1h and 1i. Therefore, some of the reasons of the no yield of
O–H insertion products form 1h and 1i were attributed to the
stability of DNQ under the reaction conditions and reactivity of
its Rh carbene complex. However, we presume the main reason
instability of the expected products, 1,2-naphthalenediols 4h and
4i, under the reaction conditions. Because, we confirmed the
decomposition of 4h under the reaction conditions. In addition,
we also confirmed that Rh-catalyzed O-H insertion reaction of
alcohol with same DNQ 1h and 1i proceeded to afford mono
alkyl ethers of 1,2-naphthalenediol which were not decomposed
under the reaction conditions (vide infra, Table 2 runs 20-22).11
This result suggested DNQ 1h and 1i and its Rh carbenes have
adequate life-time for the O-H insertion reaction in the reaction
conditions.
Similarly, various 3-carbonyl group substituted DNQ reacted
with alcohol to give O–H insertion reaction as shown in runs 11–
19. Introduction of methyl group or phenylgroup at C-4 positions
did not drag down for the O–H insertion reaction (runs 18 and
19).
Table 1. Rh-catalyzed O–H insertion reaction of 3-alkoxycarbonyl-
1,2-diazonaphthoquinone 1.a
In contrast to the reaction with water, O–H insertion products
were obtained in high yields by reacting 3-unsubstituted/3-alkyl
group substituted DNQs and alcohol (Table 2, runs 20–25 versus
Table 1, runs 7 and 8).
The O–H insertion reaction is also examined for 1-diazotized
DNQ 2 (Table 3).
In case of the reaction with water, O–H insertion products
Run
1
2
R
CO2Pr
CO2Me
CO2Et
CO2Allyl
CO2Bn
CHO
1
4
Time (h)
Yield (%)
1a
1b
1c
1d
1e
1f
4a
4b
4c
4d
4e
4f
7
5.5
5
quant.
quant.
78
were
not
obtained
from
3-unsubstituted
and 3-
3
trifluoromethanesulfonyl DNQ 2a and 2b (runs 1 and 2), while
naphthalenediol 4b was obtained from 3-methoxylcarbonyl DNQ
2c (run 3). By the reaction with methanol with DNQ 2a-c, O–H
insertion product was obtained in high yields (runs 4–6). O-H
insertion product 7d was also formed by the reaction with
propargyl alcohol (run 7).
4
5
8
9
64
84
6
7
76
73
7
CONHPh
H
Me
1g
1h
1i
4g
4h
4i
6.5
1
1
8
9
0
0
a Reaction conditions: 3.0 mol% Rh2(OAc)4 in benzene (0.01 M for 1) at 60
°C.
Table 2. Rh-catalyzed O-H insertion reaction of 1,2-diazonaphthoquinones 1 with various alcohol.a
Run
1
R1
CO2Me
CO2Me
CO2Me
CO2Me
CO2Me
CO2Me
CO2Me
CO2Me
CO2Me
CO2Me
CO2Pr
CO2Pr
CO2Pr
CO2Bn
CO2Ph
CHO
R2
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
H
Me
Ph
H
H
H
H
H
H
1
1b
1b
1b
1b
1b
1b
1b
1b
1b
1b
1a
1a
1a
1e
1j
R3OH (equiv.)
MeOH (30)
EtOH(30)
time (h)
8
5
yield (%)
88
88
5a
5b
5c
5d
5e
5f
5g
5h
5i
2
9
3
4
PrOH(30)
BnOH (5)
7.5
8
92
86
5
t-BuOH (5)
PhOH (1)
9.5
15.5
10.5
21
8
72
72
60
6
7
MeCO2CH2OH (5)
CH2=CHCH2OH (30)
≡CCH
8
40
9
HC
2OH (30)
20b
63
10c
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
(CH2OH)2 (5)
14
10
8
5j
MeOH (30)
BnOH(5)
≡CCH
5k
5l
88
95
2 d
94
72
HC
2OH (30)
9.5
6.5
9.5
7
12
5.5
8
5m
5n
5o
5p
5q
5r
5s
MeOH(30)
MeOH (30)
MeOH (30)
MeOH (30)
MeOH (30)
MeOH (30)
MeOH(30)
MeOH (30)
BnOH(5)
1f
83
99
CONHPh
CO2Me
CO2Me
H
1g
1k
1l
79
77
1h
1i
4.5
11
4.5
7
4
4.5
5t
78
85
Me
Me
5u
5v
5w
5x
5y
1i
97
95
88
quant.
i-Pr
CH2OTBS
CH2OTBS
1m
1n
1n
MeOH (30)
MeOH (30)
BnOH(5)
a Reaction conditions: 3.0 mol% Rh2(OAc)4 in benzene (0.01 M for 1) at 60 °C.
b 6a was obtained in 72% yield.
c Reaction mixture was 0.02 M.
d 6b was obtained in 76% yield.

3
2. (a) Platt KL, Oesch F. J. Org. Chem. 1983; 48: 265;
(b) Zambrao JL, Dorta R. Synlett 2003; 1545
(c) Crandall JK, Zucco M, Kircch RS, Coppert DM. Tetrahedron
Lett. 1991; 32: 5441.
Table 3. Rh-catalyzed O–H insertion reaction of 3-alkoxycarbonyl-
1,2-diazonaphthoquinone 2a.
3. For reviews, see: (a) Kitamura M. J. Synth. Org. Chem., Jpn.
2014; 72: 14;
(b) Kitamura M. Chem. Rec. DOI: 10.1002/tcr.201600118;
(c) Othman DIA, Kitamura M. Heterocycles, 2016; 92: 1761.
4. (a) Kitamura M, Tashiro N, Sakata R, Okauchi T. Synlett 2010;
2503;
(b) Kitamura M, Sakata R, Tashiro N, Ikegami A, Okauchi T. Bull.
Chem. Soc. Jpn., 2015; 88: 824.
Run
R1
2
R2
time
(h)
0.5
2.5
1
product
yield
(%)
0
5. (a) Reiser A, Shilh HY, Yeh TF, Huang JP. Angew. Chem. Int. Ed,
1996; 35: 2428;
1
2
3
4
5
6
7
H
OTf
2a
2b
2c
2a
2b
2c
2c
H
H
4h
4j
(b) Reiser A, Huang JP, He X, Yeh TF, Jha S, Shih HY, Kim MS,
Han YK, Yan K. Eur. Polym. J. 2002; 38: 619;
(c) Fukukawa K-i, Ueda M. Polym. J. 2008; 40: 281.
6. (a) Kitamura M, Sakata R, Okauchi T. Tetrahedron Lett. 2011; 52:
1931;
0
CO2Me
H
OTf
H
4b
7a
7b
7c
7d
67
86
86
97
91
Me
Me
Me
≡CCH
3
3
CO2Me
CO2Me
1
(b) Kitamura M, Kisanuki M, Sakata R, Okauchi T. Chem. Lett.
2011; 40: 1129;
b
HC
3
2
a Reaction conditions: 3.0 mol% Rh2(OAc)4 in benzene (0.01 M for 2) at 60
(c) Kitamura M, Kisanuki M, Okauchi T. Eur. J. Org. Chem.
2012; 905;
°C.
b MS 4A was added in reaction mixture.
(d) Kitamura M, Araki K, Matsuzaki H, Okauchi T. Eur. J. Org.
Chem. 2013; 5045: 35;
(e) Kitamura M, Kubo K, Yoshinaga S, Matsuzaki H, Ezaki K,
Matsuura T, Matsuura D, Fukuzumi N, Araki K, Narasaki M.
Tetrahedron Lett. 2014; 55: 1653;
(f) Kitamura M, Kisanuki M, Kanemura K, Okauchi T. Org. Lett.
2014; 16: 1554;
In Scheme 3, possible reaction mechanism is depicted for the
Rh2(OAc)4-catalyzed formation of naphthalenediol derivatives
from DNQ 1 by reaction with alcohol. We confirmed that the O–
H insertion reaction did not proceed in the absence of Rh(II)
catalyst, and the reaction was not affected strongly in the
presence of radical-trap reagent such as TEMPO (2,2,6,6-
tetramethylpiperidine 1-oxyl).12 Therefore, we suppose this O–H
insertion reaction proceeds via Rh(II) carbene as intermediate.
First, Rh2(OAc)4 reacts with DNQ 1 to form Rh(II) carbene
complex I. Nucleophilic attack of alcohol on carbene complex I
proceeds to form oxonium ylide II, and then aromatization and
deprotonation proceeds to form 5 with releasing Rh2(OAc)4.
(g) Kitamura M, Takahashi S, Okauchi T. J. Org. Chem. 2015; 80:
8406;
7. Recent reaction of diazonaphthoquinone by other groups, see: (a)
Bahadur K, Magar S, Lee YR. Org. Lett. 2013; 15: 4288.
(b) Baral EKR, LeeYR, Kim SH. Adv. Synth. Catal. 2015; 357:
2883;
(c) Baral EKR, Lee YR, Kim SH, Wee YJ. Synthesis 2016; 48,
579.
8. For reviews of metal-catalyzed reaction of diazo compounds, see:
(a) Padwa A, Krumpe KE. Tetrahedron 1992; 48: 5385;
(b) Ye T, McKervey MA. Chem. Rev. 1994; 94: 1091;
(c) Doyle M. P.; Ye, T.; McKervey, M. A. Modern Catalytic
Methods for Organic Synthesis with Diazo Compounds; John
Wiley & Sons: New York, 1998;
(d) Davies HML, Beckwith RE. J. Chem. Rev. 2003; 103: 2861;
(e) Zhang Z, Wang J. Tetrahedron 2008; 64: 6577;
(f) Doyle MP, Duffy R, Ratnikov M, Zhou L. Chem. Rev. 2010;
110: 704.
9. Rh-catalyzed O–H insertion reaction of diazocarbonyl compounds
with water or alcohols, see: (a) Paulissen R, Reimlinger H, Hayez
E, Hubert AJ, Teyssié P. Tetrahedron Lett. 1973; 2233;
(b) Noels AF, Demonceau A, Petiniot N, Hubert AJ, Teyssié P.
Tetrahedron 1982; 38: 2733;
Scheme 3. Plausible reaction mechanism.
(c) Bulugahapitiya P, Landais. Y, Parra-Rapado L, Planchenault
D, Weber V. J. Org. Chem. 1997; 62: 1630.
10. We reported several methods for the synthesis of protected 1,2-
naphthalenediols by metal-catalyzed reaction of
diazonaphthoquinones: see ref. 6b,c,f.
11. Stability of naphthalenediols and naphthols, see:
(a) Foti, MC, Johnson ER, Vinqvist MR, Wright JS, Barclay LRC,
Ingold, KU. J. Org. Chem. 2002; 67: 5190;
In conclusion, we developed the Rh2(OAc)4-catalyzed
synthesis of 1,2-naphthalenediol derivatives by the reaction of
DNQs with water/alcohol.
Acknowledgments
(b) Pino E, Aspée A, López-Alarcón C, Lissi E. J. Phys. Org.
Chem. 2006; 19: 867.
This work was supported by JSPS KAKENHI Grant Number
26410054.
12. When 1 equiv. of TEMPO was added in the same reaction
conditions of Table 2, Run 2, O-H insertion product 5a was
obtained in 81% and DNQ 1b was recovered in 7 % after stirring
for 11 h.
References and notes
Supplementary Material
1. (a) Stahl P, Kissau L, Mazitschek R, Huwe A, Furet P, Giannis A,
Waldmann H. J. Am. Chem. Soc. 2001; 123: 11586;
(b) Lu T, Shao P, Mathew L, Sand A, Sun W. J. Am. Chem. Soc.
2008; 130: 15782;
Supplementary data associated with this article can be found,
in the online version.
(c) Madan S, Cheng C. J. Org. Chem. 2006; 71: 8312.

4
Tetrahedron
1,2-Napthalendiols were synthesized from
diazonaphthoquinone.
1,2-Napthalendiol mono-protected alcohols were
selectively synthesized.
Various alcohols and water were used as the
reactants.