Formation of an exceptionally stable ketene during phototransformations of bicyclo[2.2.2]oct-5-en-2-ones having mixed chromophores

被引：1

作者：

Ghosh, Asitanga ^{[1
]}

机构：

[1] Hooghly Mohsin Coll, Dept Chem, Hooghly 712101, W Bengal, India

来源：

BEILSTEIN JOURNAL OF ORGANIC CHEMISTRY | 2020年 / 16卷

关键词：

alpha; beta- and beta; gamma-enones; bridgehead position; ketene; mixed chromophores; DI-PI-METHANE; PHOTOCHEMICAL-TRANSFORMATIONS; CIS-1,2-DIBENZOYLALKENES; REARRANGEMENTS; SELECTIVITY; PHOTOLYSIS; BETA;

D O I：

10.3762/bjoc.16.190

中图分类号：

O62 [有机化学];

学科分类号：

070303 ; 081704 ;

摘要：

Photochemical reactions of bicyclo[2.2.2]oct-5-en-2-ones having mixed chromophores like a 5,6 dibenzoyl moiety and bulky electron-deficient substituents like phenyl or isopropenyl at the bridgehead position were analyzed for the first time in different solvents and upon irradiation with different wavelengths. In all cases, a regioselective photoinduced 1,5-phenyl migration leading to vinyl ketenes from the more congested site of the molecule to the less congested one has been observed. The ketenes were exceptionally stable both in air and solution. Its stability studies in acetonitrile through time-dependent UV absorption spectra revealed that it remained almost unchanged at least for a couple of weeks.

引用

页码：2297 / 2303

页数：7

共 50 条

[41] A new pathway to substituted 6-chloro-2-pyridinecarboxylic acid derivatives from the reaction of 4,6-dichloro-2-oxa-5-azabicyclo[2.2.2]oct-5-en-3-ones with nucleophiles.
Dubois, KJ
Hoornaert, GJ
TETRAHEDRON, 1996, 52 (20) : 6997 - 7002
[42] Rearrangement approaches to cyclic skeletons.: XIII.: Total synthesis of triquinane sesquiterpenes, (±)-modhephene, and (±)-isocomene, on the basis of formal substitution at both bridgeheads of a bicyclo[2.2.2]oct-5-en-2-one
Uyehara, T
Murayama, T
Sakai, K
Onda, K
Ueno, M
Sato, T
BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN, 1998, 71 (01) : 231 - 242
[43] The oxa-di-pi-methane photochemical rearrangement of the quinuclidinones, 1-and 2-aza-3-carboxybicyclo[2.2.2]oct-2-en-5-ones: Application to the synthesis of pyrrolizidine alkaloids.
McClure, CK
Link, JS
Kiessling, A
ABSTRACTS OF PAPERS OF THE AMERICAN CHEMICAL SOCIETY, 2001, 221 : U181 - U181
[44] REARRANGEMENT APPROACHES TO CYCLIC SKELETONS .8. TOTAL SYNTHESIS OF (+/-)-NAKAFURAN-8, A MARINE METABOLITE WITH ANTIFEEDANT PROPERTIES, ON THE BASIS OF BRIDGEHEAD SUBSTITUTION OF A BICYCLO[2.2.2]OCT-5-EN-2-ONE SYSTEM
UYEHARA, T
SUGIMOTO, M
SUZUKI, I
YAMAMOTO, Y
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1992, (14): : 1785 - 1788
[45] Vibrational Spectra and Stable Conformations of (1RS, 5RS, 6SR)-6-Methoxycarbonylamino-(5'-methoxyindolo[2,3-b])bicyclo[3.2.1]oct-2-en
Davydova, I. B.
Senyavin, V. M.
Zefirova, O. N.
Kuramshina, G. M.
RUSSIAN JOURNAL OF PHYSICAL CHEMISTRY A, 2019, 93 (08) : 1525 - 1536
[46] Vibrational Spectra and Stable Conformations of (1RS, 5RS, 6SR)-6-Methoxycarbonylamino-(5'-methoxyindolo[2,3-b])bicyclo[3.2.1]oct-2-en
I. B. Davydova
V. M. Senyavin
O. N. Zefirova
G. M. Kuramshina
Russian Journal of Physical Chemistry A, 2019, 93 : 1525 - 1536
[47] Rearrangement Approaches to Cyclic Skeletons. XIII. Total Synthesis of Triquinane Sesquiterpenes, ( QQ )-@Modhephene, and ( QQ )-@Isocomene, on the Basis of Formal Substitution at Both Bridgeheads of a Bicyclo[2.2.2]oct-@5-@en-@2-@one
Uyehara, T.
Murayama, T.
Sakai, K.
Onda, K.
Bulletin of the Chemical Society of Japan, 1998, 71 (01)
[48] A New Pathway to Substituted 6-Chloro-2-pyridinecarboxylic Acid Derivatives from the Reaction of 4,6-Dichloro-2-oxa-5-aza-bicyclo[2.2. 2]oct$ MIN@5-en-3-ones with Nucleophiles
Dubois, K. J.
Hoornaert, G. J.
Tetrahedron, 52 (20):
[49] STABLE CARBOCATIONS OF THE BENZOCYCLENE SERIES .4. STUDY ON 5-METHYL-2,3-TETRAFLUOROBENZOBICYCLO[2.2.2]OCT-2-EN-5-YL-CATIONS AND ITS CONVERSIONS UNDER THE CONDITIONS OF SHORT AND LONG LIFETIMES
KAMSHII, GT
MAMATYUK, VI
SPIVAK, AY
BARKHASH, VA
ZHURNAL ORGANICHESKOI KHIMII, 1979, 15 (06): : 1221 - 1231
[50] RIFM fragrance ingredient safety assessment, 1-[5(Or 6)-methyl-7(or 8)-(1-methylethyl)bicyclo[2.2.2]oct-5-en-2-yl]ethan-1-one, CAS Registry Number 68259-33-6
Api, A. M.
Belsito, D.
Botelho, D.
Bruze, M.
Burton, G. A., Jr.
Buschmann, J.
Cancellieri, M. A.
Dagli, M. L.
Date, M.
Dekant, W.
Deodhar, C.
Fryer, A. D.
Jones, L.
Joshi, K.
Kumar, M.
Lapczynski, A.
Lavelle, M.
Lee, I
Liebler, D. C.
Moustakas, H.
Na, M.
Penning, T. M.
Ritacco, G.
Romine, J.
Sadekar, N.
Schultz, T. W.
Selechnik, D.
Siddiqi, F.
Sipes, I. G.
Sullivan, G.
Thakkar, Y.
Tokura, Y.
FOOD AND CHEMICAL TOXICOLOGY, 2021, 156

← 1 2 3 4 5 →