Organic Letters
Letter
Acids with Bromoacetylenes by Hypervalent Iodine Reagent
Catalysis: A Facile Approach to Ynones. Angew. Chem., Int. Ed.
2015, 54, 8374. (c) Li, L.; Mu, X.; Liu, W.; Wang, Y.; Mi, Z.; Li, C.-J.
Simple and Clean Photoinduced Aromatic Trifluoromethylation
Reaction. J. Am. Chem. Soc. 2016, 138, 5809. (d) Xie, X.; Li, P.;
Shi, Q.; Wang, L. Visible-light-induced tandem cyclization of 2-
alkynylanilines with disulfides: a convenient method for accessing
benzothiophenes under transition-metal-free and photocatalyst-free
conditions. Org. Biomol. Chem. 2017, 15, 7678.
complexes of quinuclidine and diazabicyclo [2.2.2]octane with carbon
tetrabromide. J. Org. Chem. 1987, 52, 1451. (c) Cavallo, G.;
Metrangolo, P.; Milani, R.; Pilati, T.; Priimagi, A.; Resnati, G.;
Terraneo, G. The Halogen Bond. Chem. Rev. 2016, 116, 2478.
(d) Sun, C.; Chang, W.; Ma, W.; Chen, C.; Zhao, J. Photoreductive
Debromination of Decabromodiphenyl Ethers in the Presence of
Carboxylates under Visible Light Irradiation. Environ. Sci. Technol.
2013, 47, 2370.
(24) (a) Semenov, S. N.; Belding, L.; Cafferty, B. J.; Mousavi, M. P.
S.; Finogenova, A. M.; Cruz, R. S.; Skorb, E. V.; Whitesides, G. M.
Autocatalytic Cycles in a Copper-Catalyzed Azide−Alkyne Cyclo-
addition Reaction. J. Am. Chem. Soc. 2018, 140, 10221. (b) Ferrer
Flegeau, E.; Bruneau, C.; Dixneuf, P. H.; Jutand, A. Autocatalysis for
C−H Bond Activation by Ruthenium(II) Complexes in Catalytic
Arylation of Functional Arenes. J. Am. Chem. Soc. 2011, 133, 10161.
(c) Bissette, A. J.; Fletcher, S. P. Mechanisms of Autocatalysis. Angew.
Chem., Int. Ed. 2013, 52, 12800.
(12) Lima, C. G. S.; de M. Lima, T.; Duarte, M.; Jurberg, I. D.;
Paixao, M. W. Organic Synthesis Enabled by Light-Irradiation of EDA
̃
Complexes: Theoretical Background and Synthetic Applications. ACS
Catal. 2016, 6, 1389.
(13) Postigo, A. Electron Donor-Acceptor Complexes in Perfluor-
oalkylation Reactions. Eur. J. Org. Chem. 2018, 2018, 6391.
(14) (a) Foster, R. Electron donor-acceptor complexes. J. Phys.
Chem. 1980, 84, 2135. (b) Rosokha, S. V.; Kochi, J. K. Fresh Look at
Electron-Transfer Mechanisms via the Donor/Acceptor Bindings in
the Critical Encounter Complex. Acc. Chem. Res. 2008, 41, 641.
(c) Hilinski, E. F.; Masnovi, J. M.; Amatore, C.; Kochi, J. K.;
Rentzepis, P. M. Charge-transfer excitation of electron donor-acceptor
complexes. Direct observation of ion pairs by time-resolved
(picosecond) spectroscopy. J. Am. Chem. Soc. 1983, 105, 6167.
(d) Hubig, S. M.; Bockman, T. M.; Kochi, J. K. Optimized Electron
Transfer in Charge-Transfer Ion Pairs. Pronounced Inner-Sphere
Behavior of Olefin Donors. J. Am. Chem. Soc. 1996, 118, 3842.
(e) Mulliken, R. S. Molecular compounds and their spectra. III. The
interaction of electron donors and acceptors. J. Phys. Chem. 1952, 56,
801.
(15) Fox, M. A.; Younathan, J.; Fryxell, G. E. Photoinitiation of the
SRN1 reaction by excitation of charge-transfer complexes. J. Org.
Chem. 1983, 48, 3109.
(16) Sankararaman, S.; Haney, W. A.; Kochi, J. K. Aromatic nitration
with ion radical pairs [ArH.cntdot.+,NO2.cntdot.] as reactive
intermediates. Time-resolved studies of charge-transfer activation of
dialkoxybenzenes. J. Am. Chem. Soc. 1987, 109, 5235.
̈
(25) Bo
hm, A.; Bach, T. Radical Reactions Induced by Visible Light
nig’s Base: Synthetic Applications
in Dichloromethane Solutions of Hu
̈
and Mechanistic Observations. Chem. - Eur. J. 2016, 22, 15921.
(26) (a) Taft, R. W. Progress in Physical Organic Chemistry; Wiley:
́
2009. (b) Guieu, V.; Izquierdo, A.; Garcia-Alonso, S.; Andre, C.;
Madaule, Y.; Payrastre, C. Fluorescent Streptocyanine Dyes: Synthesis
and Photophysical Properties − Synthesis of a New Hemi-
carboxonium Salt. Eur. J. Org. Chem. 2007, 2007, 804.
(27) (a) Raghavachari, R. Near-Infrared Applications in Biotechnology;
Taylor & Francis: 2000. (b) Bricks, J. L.; Kachkovskii, A. D.;
Slominskii, Y. L.; Gerasov, A. O.; Popov, S. V. Molecular design of
near infrared polymethine dyes: A review. Dyes Pigm. 2015, 121, 238.
(c) Ishchenko, A. A. Structure and spectral-luminescent properties of
polymethine dyes. Russ. Chem. Rev. 1991, 60, 865.
(28) (a) Shindy, H. A. Fundamentals in the chemistry of cyanine
dyes: A review. Dyes Pigm. 2017, 145, 505. (b) Panigrahi, M.; Dash,
S.; Patel, S.; Mishra, B. K. Syntheses of cyanines: a review. Tetrahedron
2012, 68, 781. (c) Hunger, K. Industrial Dyes: Chemistry, Properties,
Applications; Wiley: 2007.
(29) (a) Le Guennic, B.; Jacquemin, D. Taking Up the Cyanine
Challenge with Quantum Tools. Acc. Chem. Res. 2015, 48, 530.
(b) Lenhard, J. R.; Cameron, A. D. Electrochemistry and electronic
spectra of cyanine dye radicals in acetonitrile. J. Phys. Chem. 1993, 97,
(17) Tobisu, M.; Furukawa, T.; Chatani, N. Visible Light-mediated
Direct Arylation of Arenes and Heteroarenes Using Diaryliodonium
Salts in the Presence and Absence of a Photocatalyst. Chem. Lett.
2013, 42, 1203.
4916. (c) Schreiber, M.; Buß, V.; Fulscher, M. P. The electronic
̈
(18) Davies, J.; Booth, S. G.; Essafi, S.; Dryfe, R. A. W.; Leonori, D.
Visible-Light-Mediated Generation of Nitrogen-Centered Radicals:
Metal-Free Hydroimination and Iminohydroxylation Cyclization
Reactions. Angew. Chem., Int. Ed. 2015, 54, 14017.
spectra of symmetric cyanine dyes: A CASPT2 study. Phys. Chem.
Chem. Phys. 2001, 3, 3906. (d) Gayton, J. N.; Autry, S.; Fortenberry,
R. C.; Hammer, N. I.; Delcamp, J. H. Counter Anion Effect on the
Photophysical Properties of Emissive Indolizine-Cyanine Dyes in
Solution and Solid State. Molecules 2018, 23, 3051. (e) Levitz, A.;
Marmarchi, F.; Henary, M. Introduction of various substitutions to
the methine bridge of heptamethine cyanine dyes Via substituted
dianil linkers. Photochem. Photobiol. Sci. 2018, 17, 1409. (f) Taniguchi,
M.; Lindsey, J. S. Database of Absorption and Fluorescence Spectra of
> 300 Common Compounds for use in PhotochemCAD. Photochem.
Photobiol. 2018, 94, 290.
́
́
(19) Arceo, E.; Jurberg, I. D.; Alvarez-Fernandez, A.; Melchiorre, P.
Photochemical activity of a key donor−acceptor complex can drive
stereoselective catalytic α-alkylation of aldehydes. Nat. Chem. 2013, 5,
750.
(20) Franz, J. F.; Kraus, W. B.; Zeitler, K. No photocatalyst required
− versatile, visible light mediated transformations with polyhalo-
methanes. Chem. Commun. 2015, 51, 8280.
(21) (a) Raghunadh, A.; Meruva, S. B.; Kumar, N. A.; Kumar, G. S.;
Rao, L. V.; Syam Kumar, U. K. An Efficient and Practical Synthesis of
Aryl and Hetaryl α-Keto Esters. Synthesis 2012, 2012, 283.
(b) Lenihan, B. D.; Shechter, H. Chemistry of Conversions of [o-
[1-Halo-1-(p-tolylsulfonyl)alkyl]benzyl]trimethylsilanes to o-Quino-
dimethanes and Benzocyclobutenes. J. Org. Chem. 1998, 63, 2086.
(c) Zhang, G.-B.; Wang, F.-X.; Du, J.-Y.; Qu, H.; Ma, X.-Y.; Wei, M.-
X.; Wang, C.-T.; Li, Q.; Fan, C.-A. Toward the Total Synthesis of
Palhinine A: Expedient Assembly of Multifunctionalized Isotwistane
Ring System with Contiguous Quaternary Stereocenters. Org. Lett.
2012, 14, 3696. (d) 5,5-Dibromo-2,2-dimethyl-1,3-dioxane-4,6-dione.
In Encyclopedia of Reagents for Organic Synthesis; John Wiley & Sons
Ltd.: 2001.
(30) (a) Ryzhova, O.; Tarabara, U.; Trusova, V.; Kurutos, A. In
Aggregation of cyanine dyes in lipid environment, 2015 International
Young Scientists Forum on Applied Physics (YSF), 29 Sept.−2 Oct.
2015; 2015; p 1. (b) Lu, T.; Lin, Z.; Ren, J.; Yao, P.; Wang, X.; Wang,
Z.; Zhang, Q. The Non-Specific Binding of Fluorescent-Labeled
MiRNAs on Cell Surface by Hydrophobic Interaction. PLoS One
2016, 11, No. e0149751.
(31) Miyamoto, N.; Kuroda, K.; Ogawa, M. Visible Light Induced
Electron Transfer and Long-Lived Charge Separated State in Cyanine
Dye/Layered Titanate Intercalation Compounds. J. Phys. Chem. B
2004, 108, 4268.
(32) (a) Zhao, J.; Chen, C.; Ma, W. Photocatalytic Degradation of
Organic Pollutants Under Visible Light Irradiation. Top. Catal. 2005,
35, 269. (b) Yang, S.; Tian, H.; Xiao, H.; Shang, X.; Gong, X.; Yao, S.;
Chen, K. Photodegradation of cyanine and merocyanine dyes. Dyes
Pigm. 2001, 49, 93. (c) Toutchkine, A.; Nguyen, D.-V.; Hahn, K. M.
Merocyanine Dyes with Improved Photostability. Org. Lett. 2007, 9,
(22) A UV−vis study is included in the SI.
(23) (a) Here, the EDA complex is likely enabling halogen bonding
interaction between the haloalkane and amine. (b) Blackstock, S. C.;
Lorand, J. P.; Kochi, J. K. Charge-transfer interactions of amines with
tetrahalomethanes. X-ray crystal structures of the donor-acceptor
F
Org. Lett. XXXX, XXX, XXX−XXX