+

3a
3a'
1
H NMR
GC of 3a and 3a
Mechanisms of Phenylchlorocarbene Additions to Dibenzocyclooctadiyne,
Dinaphthocyclooctadiyne, and Dinaphthocyclooctadiene

Elizabeth Dalchand, Alison Scorese, Karol Francisco, Dina C. Merrer
*



Department of Chemistry, Barnard College, 3009 Broadway, New York, NY 10027
Ongoing and Future Work
Introduction
Acknowledgments
Howard Hughes Medical Institute Internship (E.D.)
National Science Foundation (CHE-0844034)
ACS Petroleum Research Fund (52099-UR4)
Con Edison Summer Internship Program (K.F.)
Camilla Buzard (Barnard College)
Prof. Colin Nuckolls (Columbia University)
Dr. Brandon Fowler (Columbia University)
Barnard College Chemistry Department
Attempted Aromatization of 3a 4a with DDQ
After the [2+2+2+2] cycloaddition of 1,7-octadiyne (2a), the reaction mixture was
examined via GC/MS. Three compounds were detected, with the following
retention times: 8.7 min (m/z 220), 9.7 min (m/z 212), and 10.2 min (m/z 212). The
compounds with t
R
= 9.7 and 10.2 min had molecular ions consistent with the
molecular weight of the desired product, 4a.
Aromatization of compound
3a 4a was attempted with
DDQ. Regardless of the
reaction temperature (60 C,
100 C, or 125 C), desired
aromatized product 4a was
produced in very low yield.
?
Wender, P. A.; Christy, J. P. J. Am. Chem. Soc. 2007, 129, 13402-13403.
Wender, P. A.; Lesser, A. B.; Sirois, L. E. Angew. Chem. Int. Ed. 2012, 51, 2736-2740.
Fowler, B.; Nuckolls, C. Personal communication, 2014.
GC of 3a 4a Reaction Mixture
The Merrer group endeavors to determine the mechanisms of carbene additions to
strained substrates: reactions that may be under dynamic control. Multistep
syntheses of strained dinaphthocyclooctadiene (4b), dibenzocyclooctadiyne (5a),
and dinaphthocyclooctadiyne (5b) are being conducted from their respective diynes
(2a and 2b). We have synthesized 4b and are currently pursing the conversion of
4b 5b. We believe we have synthesized 4a, yet are exploring alternate routes to
it; we will then convert 4a 5a.
Synthesis of Dibenzocyclooctadiyne
The
1
H NMR and
13
C NMR spectra of
the compound with a GC/MS retention
time of 9.7 min (m/z 212) contained
resonances belonging to 3a and 3a.
The compounds have the same
retention time and the same m/z values,
and cannot be separated from each
other via column chromatography or gas
chromatography.
1
H NMR
Synthesis of Dinaphthocyclooctatetraene and Diyne Analog
Wender, P. A.; Christy, J. P. J. Am. Chem. Soc. 2007, 129, 13402-13403.
Wender, P. A.; Lesser, A. B.; Sirois, L. E. Angew. Chem. Int. Ed. 2012, 51, 2736-2740.
Fowler, B.; Nuckolls, C. Personal communication, 2014.
An alternative route to 2b employs Grignard chemistry. This route avoids a
deprotection step.

Once synthesized, the photolysis of each of 4b, 5a and 5b will be conducted with
phenylchlorocarbene.
Tallemite, S.; Fichou, D. Eur. J. Org. Chem. 2004, 4981-4984.
An alternative aromatization of 3a 4a is in process. This step would replace the
DDQ step in synthesizing 5a and could potentially produce a greater yield of 4a.
4a
Our initial attempts at the bromination of 4b were not successful. Due to the
persistent 1,2-bis(3-trimethylsilyl-2-propynyl)benzene impurity, it is likely that the
bromine may have reacted with the impurity rather than with 4b. Alternative
methods to produce 5b are currently under investigation.
Br
Br
BrMg SiMe3
CuI, THF
2. AgOTf
1.
acetone/H2O/CH2Cl2
H2O, THF
60
o
C
, Zn
0
O
Ni
O Br
Br
DDQ
toluene
1. Br2, CH2Cl2, -78
o
C
2. t-BuOK, THF
5b
1
2b
3b
4b
H2O, THF
60
o
C
, Zn
0
O
Ni
O Br
Br
DDQ
toluene
-or-
2a
3a
3a'
4a
1. Br2, CH2Cl2, -78
o
C
2. t-BuOK, THF
5a
CuCl2 ,DMF
Pd
2+
F3C O
-
O
3a 4a
Ph Cl
7
-or-
-or-
4b
5a
5b
8a (monocyclopropyl)
9a (dicyclopropyl)
Cl Ph
Ph Cl
Cl Ph
Ph Cl
8b (monocyclopropyl)
9b (dicyclopropyl)
-or-
Cl Ph
Ph Cl
8c (monocyclopropyl)
9c (dicyclopropyl)
-or-
Ph Cl
N N
h
6
350 nm
13
C NMR
Br2, CH2Cl2, -78
o
C
4b'
4b
Br Br
Br Br
Only the protons on the outermost six-membered ring of 4b gave the characteristic
multiplet signals of aromatic compounds; the signals corresponding to all other
protons were singlets.
13
C NMR
3a 3a
+
3a
3a'
3a 3a 3a
3a 3a 3a 3a
+
3a
3a'
CDHCl2
HOD
Horrillo-Martinez, P.; Virolleaud, M.; Jaekel, C. Chem Cat. Chem, 2010, 2, 175-181.
d b c a
Br
Br
BrMg H
CuI, THF
1 2b
I
I
10
NaI
CH2Cl2
2 1 4 6 5 3
CD2Cl2