Convenient preparation of chiral trans-9,10-dihydrophenanthrene-9,10- diamine

Article abstract of DOI:10.1080/00397910902898544

Chiral trans-9,10-dihydrophenanthrene-9,10-diamine was conveniently prepared from biphenyl-2,2'-dialdehyde using intramolecular imino pinacol coupling and oxidative cleavage of aminoalcohol as key steps.

Full text of DOI:10.1080/00397910902898544

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Convenient Preparation
of Chiral trans-9,10-
Dihydrophenanthrene-9,10-
diamine
Shuang-Zheng Lin a & Tian-Pa You a
a Department of Chemistry , University of Science
and Technology of China , Hefei, China
Published online: 16 Oct 2009.
To cite this article: Shuang-Zheng Lin & Tian-Pa You (2009) Convenient Preparation of
Chiral trans-9,10-Dihydrophenanthrene-9,10-diamine, Synthetic Communications: An
International Journal for Rapid Communication of Synthetic Organic Chemistry, 39:22,
4133-4138, DOI: 10.1080/00397910902898544
To link to this article: http://dx.doi.org/10.1080/00397910902898544
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Synthetic Communications1, 39: 4133–4138, 2009
Copyright # Taylor & Francis Group, LLC
ISSN: 0039-7911 print=1532-2432 online
DOI: 10.1080/00397910902898544
Convenient Preparation of Chiral
trans-9,10-Dihydrophenanthrene-9,10-diamine
Shuang-Zheng Lin and Tian-Pa You
Department of Chemistry, University of Science and Technology of China,
Hefei, China
Abstract: Chiral trans-9,10-dihydrophenanthrene-9,10-diamine was conveniently
prepared from biphenyl-2,20-dialdehyde using intramolecular imino pinacol
coupling and oxidative cleavage of aminoalcohol as key steps.
Keywords: trans-9,10-Dihydrophenanthrene-9,10-diamine, imino pinacol coupling,
oxidative cleavage, salen, vicinal diamine
INTRODUCTION
The vicinal diamines have found widespread applications in asymmetric
synthesis.[1] Among them, trans-1,2-diaminocyclehexane 1 and trans-
1,2-diphenyl-ethylenediamine 2 (Scheme 1) represent two successful
examples whose derivatives are widely employed as chiral ligands as well
as organocatalysts.[2–5] Therefore, we were interested in exploring the
synthesis and the properties of chiral trans-9,10-dihydrophenanthrene-
9,10-diamine (Scheme 1, 3), a structural hybrid of vicinal diamines 1
and 2.
Substituted chiral trans-9,10-dihydrophenanthrene-9,10-diamines
(R ¼ H) have been synthesized[6–9] and employed as chiral ligands in
enantioselective Diel–Alder reactions.[9] In this article, we report our
=
synthesis of free chiral diamine 3 (R R’¼H).
Received November 7, 2008.
Address correspondence to Shuang-Zheng Lin, Department of Chemistry,
University of Science and Technology of China, Hefei 230026, China. E-mail:
lins@mail.ustc.edu.cn
4133

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S.-Z. Lin and T.-P. You
Scheme 1. Structures of vicinal diamines.
RESULTS AND DISCUSSION
The synthetic approaches of chiral trans-9,10-dihydrophenanthrene-
9,10-diamine are outlined in Scheme 2.
Biphenyl-2,20-dialdehyde 4 was easily obtained through an Ullmann
reaction of 2-bromobenzaldehyde.[10] The formation of amino acid–
derived Schiff’s base 5 brought amino groups and chirality into the
substrate. Then, the 9,10-dihydrophenanthrene-9,10-diamine structure
was constructed by a intramolecular imino pinacol coupling to give dia-
mino diester diastereomer mixture 6, which was separated by column
chromatography to give two trans-diamino diesters 6a and 6b with
40.0% yield and 13.5% yield respectively. No cis-diamines were obtained
in our synthesis. After a failed attempt to obtain the target diamine 3
using Kise’s one-pot Pb(OAc)4 cleavage method,[11] we converted the dia-
mino diesters 6a and 6b to diamino dialcohols 7a and 7b, which were then
deprotected by the oxidation of NaIO4 to form the target diamines 3a
and 3b. In the oxidation cleavage step, no reaction occurred in the
absence of MeNH2ꢀHCl. However, use of HIO4ꢀ2H2O as an oxidant
led to no diamine product.
Scheme 2. Synthetic approaches of chiral trans-9,10-dihydrophenanthrene-9,10-
diamine.

Chiral trans-9,10-Dihydrophenanthrene-9,10-diamine
4135
Scheme 3. Preparation of salen-type Schiff’s base.
Thus, the two enantiomers of chiral unsubstituted trans-9,10-
dihydrophenanthrene-9,10-diamine can be conveniently prepared. How-
ever, this diamine quickly degenerates in solution. We then converted it to
its salen-type Schiff’s base 8 (Scheme 3) as a stable derivative immediately
after its separation from the reaction mixture of the deprotection step.
In summary, we have developed a convenient method to prepare the
two enantiomers of chiral trans-9,10-dihydrophenanthrene-9,10-diamine.
In contrast with the previous methods to synthesize this type of com-
pounds,[6,8,9] no chiral biaryl dialdehydes are needed in our method. This
method would be expected to be employed in the synthesis of other
vicinal diamines. The determination of the absolute configurations and
further investigation of their properties and applications in asymmetric
synthesis are still in process.
EXPERIMENTAL
All reactions were conducted in oven-dried glassware. NMR spectra were
measured on a Bruker 300-MHz spectrometer. Chemical shifts were
reported in parts per million (ppm) relative to internal tetramethylsilane
(TMS). Column chromatography was carried out on silica gel (200–400
mesh) using petroleum ether (60–90ꢁC) and EtOAc as eluents.
Diimine Diester (5)
A solution of biphenyl-2,20-dialdehyde (500 mg, 2.4 mmol), L-valine
methyl ester hydrochloride (797 mg, 4.8 mmol), and 0.70 ml Et3N
(5.0 mmol) in 20 ml CH2Cl2 was stirred with 2 g MgSO4 at room tempera-
ture for 24 h. After filtration, the filtrate was washed with saturated aqu-
eous NaHCO3 and dried over anhydrous MgSO4 to give 1.04 g of yellow
viscous oil as a crude product with quantitative yield.

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S.-Z. Lin and T.-P. You
Diamino Diesters (6a and 6b)
In an ice bath, the diimine diester crude product 5 was dissolved in 50 ml
freshly distilled THF, stirred with 1.6 g zinc powder (24 mmol) in an N2
atmosphere. Methanesulfonic acid (MsOH) (1.6 ml, 26 mmol) was added
at this temperature. After stirring at 0ꢁC for 12 h, the reaction was
stopped with saturated NaHCO3, filtered, and extracted with CH2Cl2.
The organic phases were combined, dried over anhydrous MgSO4, fil-
tered, and concentrated. The residue was separated by column chromato-
graphy to give two diastereomers of trans-diamino diesters 6a and 6b.
Compound 6a
26
Pale yellow viscous oil, 417 mg, 40.0% yield. ½aꢂD ¼ ꢃ95.7 (c ¼ 0.501,
1
CH2Cl2). H NMR (CDCl3): d ¼ 0.611 (br, 12H), 1,67 (br, 4H), 2.95
(br, 2H), 3.73 (s, 8H), 7.24–7.29 (m, 4H), 7.33–7.38 (m, 2H), 7.76 (d,
J ¼ 7.5 Hz, 2H). 13C NMR (CDCl3): d ¼ 18.5, 19.1, 31.6, 51.7, 60.5,
64.7, 124.2, 127.5, 131.0, 133.2, 134.9, 175.6.
Compound 6b (Less Polar than 6a)
26
Pale yellow viscous oil, 141 mg, 13.5% yield. ½aꢂD ¼ þ 102.4 (c ¼ 0.502,
CH2Cl2). 1H NMR (CDCl3): d ¼ 0.71 (d, J ¼ 6.9 Hz, 6H), 0.77 (d,
J ¼ 6.9 Hz, 6H), 1.66–1.77 (m, 2H), 1.93 (br, 2H), 3.1 (d, J ¼ 6.0 Hz,
2H), 3.48 (s, 6H), 3.71 (s, 2H), 7.22–7.24 (m, 4H), 7.31–7.36 (m, 2H),
7.78 (d, J ¼ 8.1 Hz, 2H).13C NMR (CDCl3): d ¼ 18.5, 19.2, 32.0, 51.3,
60.7, 65.5, 123.8, 127.7, 128.4, 130.5, 133.0, 136.0, 175.5.
Diamino Dialcohols (7a and 7b)
A solution of 100 mg diamino diester 6 (0.23 mmol) in 10 ml of diethyl
ether was refluxed with excess LiAlH4 for 6 h. After cooling to room
temperature, the reaction was ceased by careful addition of 1 ml water.
The ether solution was filtered, dried, and concentrated to give a colorless
solid as product (87 mg, quant.)
Compound 7a
26
Prepared from 6a. White solid, mp 51–53ꢁC. ½aꢂD ¼ ꢃ89.5 (c ¼ 0.500,
CH2Cl2). 1H NMR (CDCl3): d ¼ 0.65 (d, J ¼ 6.9 Hz, 6H), 0.73 (d,

Chiral trans-9,10-Dihydrophenanthrene-9,10-diamine
4137
J ¼ 6.9 Hz, 6H), 1.52–1.65 (m, 2H), 2.46–2.51 (m, 2H), 3.24 (dd, J ¼ 10.8,
6.3 Hz, 2H), 3.59 (dd, J ¼ 11.4, 4.2 Hz, 2H), 3.96 (s, 2H), 7.26–7.33 (m,
4H), 7.35–7.41 (m, 2H), 7.81 (d, J ¼ 7.8 Hz, 2H).13C NMR (CDCl3):
d ¼ 18.6, 19.1, 59.6, 61.0, 61.7, 124.2, 128.0, 128.7, 130.5, 132.6, 135.8.
Compound 7b
26
Prepared from 6b. Colorless viscous oil. ½aꢂD ¼ þ 115.9 (c ¼ 0.501,
CH2Cl2). 1H NMR (CDCl3): d ¼ 0.78 (d, J ¼ 6.9 Hz, 6H), 0.84 (d,
J ¼ 6.9 Hz, 6H), 1.63–1.81 (m, 2H), 1.91 (br, 2H), 2.46–2.52 (m, 2H),
3.23 (dd, J ¼ 10.5, 6.0 Hz, 2H), 3.47 (dd, J ¼ 10.8, 4.2 Hz, 2H), 3.94
(s, 2H), 7.25–7.29 (m, 4H), 7.33–7.41 (m, 2H), 7.79 (d, J ¼ 7.5 Hz, 2H).
13C NMR (CDCl3): d ¼ 18.7, 19.6, 29.4, 58.4, 61.0, 61.5, 124.4, 128.2,
128.8, 130.7, 132.7, 136.1.
Diamines (3a and 3b)
Diamino dialcohol 7 (100 mg, 0.26 mmol) was stirred in a solution of 3 ml
MeOH and 1.5 ml H2O. NaIO4 (391 mg, 1.8 mmol) and MeNH2ꢀHCl
(371 mg, 5.5 mmol) were added, and the reaction was monitored by
TLC. When the diamino dialcohol completely disappeared (about 2 h),
3 ml of 3 M NaOH were added to cease the reaction. The mixture was fil-
tered, and the filtrate was extracted three times with CH2Cl2. The CH2Cl2
phases were combined and concentrated to give a green solid as crude
diamine product. 1H NMR (CDCl3): d ¼ 2.16 (br, 4H), 3.89 (s, 2H),
7.28–7.40 (m, 4H), 7.47 (dd, J ¼ 6.9, 1.2 Hz, 2H), 7.78 (d, J ¼ 7.8 Hz,
2H). LC-MS 210.1.
Salen-Type Schiff’s Bases (8a and 8b)
The crude diamine was stirred in 5 ml MeOH with excess freshly distilled
salicylaldehyde for 1 h. After concentration, the residue was separated by
column chromatography to give salen-type Schiff’s base 8.
Compound 8a
26
Pale yellow solid, mp (decomp.) 73–75ꢁC, ½aꢂD ¼ ꢃ97.3 (c ¼ 1.02,
CH2Cl2), 38 mg, 35.0% yield, two steps from diamino dialcohol 7a. IR
(KBr, cmꢃ1): 3440, 3068, 2923, 2853, 1635, 1578, 1494, 1460, 1451,
1
1275, 1069, 752. H NMR (CDCl3): d ¼ 4.80 (s, 2H), 6.82 (t, J ¼ 7.5 Hz,

4138
S.-Z. Lin and T.-P. You
Hz, 2H), 6.92 (d, J ¼ 8.4 Hz, 2H), 7.19 (dd, J ¼ 7.8, 1.5 Hz, 2H), 7.25–7.36
(m, 6H), 7.45 (td, J ¼ 7.5, 1.2 Hz, 2H), 7.87 (d, J ¼ 7.8 Hz, 2H), 8.36 (s,
2H), 13.0 (br, 2H). 13C NMR (CDCl3): d ¼ 72.2, 117.0, 118.6, 119.0,
124.2, 127.1, 128.5, 128.8, 132.0, 132.9, 133.0, 134.7, 161.1, 168.0. HRMS
calcd. for C28H22N2O2 (Mþ) 418.1681; found 418.1680.
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