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The Journal of Organic Chemistry
HRMS (APCI, quadrupole-orbitrap) m/z: [M+H]+ calculated
ASSOCIATED CONTENT
1
2
3
4
5
6
7
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for C19H25O2: 285.1849, found: 285.1839.
1
Supporting Information
cis-ACB-1: H NMR (500 MHz, CDCl3): δ 7.26 (d, J =
1
Spectroscopic H NMR and 13C{1H} NMR for all new com-
8.8 Hz, 2H), 6.87 (d, J = 8.8 Hz, 2H), 3.80 (s, 3H), 2.91 (m,
1H), 2.36 (br s, 1H), 2.31 (m, 1H), 2.25 (d, J = 11.1 Hz, 1H),
2.20 (m, 1H), 2.11 (d, J = 11.1 Hz, 1H), 2.02 (m, 2H), 1.75
(m, 8H), 1.64 (s, 1H) ppm. 13C{1H} NMR (126 MHz,
CDCl3): δ 158.7, 142.0, 126.3, 113.9, 84.1, 55.49, 55.47,
48.5, 45.6, 41.2, 39.8, 38.3, 34.1, 32.4, 31.2, 30.1, 28.7 ppm.
HRMS (APCI, quadrupole-orbitrap) m/z: [M+H]+ calculated
for C19H25O2: 285.1849, found: 285.1838.
pounds and IR data compounds 1-10. Phosphorescence, UV-Vis
and transient absorption data along with characterization of
suspensions by DLS, SEM and PXRD for compounds 1-5. Pho-
toproduct distributions percentages for compounds 1-5 and pho-
tochemical deuteration experiments for compounds 2-4. Single
crystal X-ray thermal ellipsoid plots and crystallography data
for compounds 2-4. Calculated structure of compound 5. (PDF).
Single crystal X-ray structures for compounds 2-4 (CIF files).
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BCB-2: H NMR (500 MHz, CDCl3): δ 6.80 (s, 1H), 6.78
(s, 1H), 3.56 (d, J = 14.3 Hz, 1H), 3.10 (d, J = 14.3 Hz, 1H),
2.30 (s, 3H), 2.27 (s, 3H), 2.02 (m, 2H), 1.96 (m, 3H), 1.85
(m, 3H), 1.69 (m, 9H), 1.53 (d, J = 14.7 Hz, 1H) ppm.
13C{1H} NMR (126 MHz, CDCl3): δ 147.2, 141.5, 139.2,
131.6, 129.3, 121.6, 81.6, 50.8, 48.0, 43.8, 37.2, 34.3, 29.0,
22.1, 16.9 ppm. HRMS (APCI, quadrupole-orbitrap) m/z:
[M+H]+ calculated for C21H29O: 297.2213, found: 297.2201.
Elimination product of cis- and trans-ACB-3: 1H NMR
(500 MHz, CDCl3): δ 6.57 (s, 2H), 3.77 (s, 3H), 2.47 (m,
3H), 2.31 (m, 6H), 2.09 (m, 2H), 2.00 (m, 2H), 1.85 (m, 2H),
1.75 (m, 6H) ppm. 13C{1H} NMR (126 MHz, CDCl3): δ
157.8, 156.2, 138.2, 128.7, 122.1, 112.6, 55.1, 46.0, 43.1,
39.2, 37.0, 36.8, 31.5, 29.9, 21.1 ppm. HRMS (APCI, quad-
rupole-orbitrap) m/z: [M]+ calculated for C21H26O: 294.1978,
found: 297.1972.
AUTHOR INFORMATION
Corresponding Author
* mgg@chem.ucla.edu
Notes
ORCID:
Miguel A. Garcia-Garibay: 0000-0002-6268-1943
Vince M. Hipwell: 0000-0001-6297-241X
ACKNOWLEDGMENT
This work was supported by grants National Science Foundation
grants CHE-1855342, MRI-1532232 (solid state NMR), and
CHE-1048804 (solution NMR).
1
Elimination product of BCB-3: H NMR (500 MHz,
CDCl3): δ 6.57 (s, 1H), 6.52 (s, 1H), 5.35 (s, 1H), 3.77 (s,
3H), 3.66 (s, 2H), 2.28 (s, 3H), 2.00 (m, 3H), 1.76 (m, 6H),
1.71 (m, 6H) ppm. 13C{1H} NMR (126 MHz, CDCl3): δ
159.7, 146.0, 137.5, 133.9, 131.5, 128.7, 115.0, 105.3, 55.5,
42.9, 38.3, 36.9, 36.1, 28.6, 18.1 ppm. HRMS (APCI, quad-
rupole-orbitrap) m/z: [M]+ calculated for C21H26O: 294.1978,
found: 297.1989.
REFERENCES
(1) Yang, N. C.; Yang, D. D. H. Photochemical Reactions of
Ketones in Solution. J. Am. Chem. Soc. 1958, 80, 2913–2914.
(2) Leibovitch, M.; Olovsson, G.; Scheffer, J. R.; Trotter, J. An
Investigation of the Yang Photocyclization Reaction in the Solid
State: Asymmetric Induction Studies and Crystal Structure-
Reactivity Relationships. J. Am. Chem. Soc. 1998, 120, 12755–
12769.
(3) Cai, X.; Cygon, P.; Goldfuss, B.; Griesbeck, A. G.; Heckroth,
H.; Fujitsuka, M.; Majima, T. α-Carbonyl Substituent Effect on the
Lifetimes of Triplet 1,4-Biradicals from Norrish-Type-II Reactions.
Chem. - A Eur. J. 2006, 12, 4662–4667.
Elimination product of trans-ACB-4: 1H NMR (500
MHz, CDCl3): δ 7.20 (d, J = 8.0 Hz, 1H), 7.12 (d, J = 1.7
Hz, 1H), 7.01 (dd, J = 8.0, 1.7 Hz, 1H), 3.38 (sept, J = 6.9
Hz, 1H), 2.87 (sept, J = 6.9 Hz, 1H), 2.85 (m, 1H), 2.57 (s,
2H), 2.08 (m, 2H), 1.97 (m, 2H), 1.89 (m, 2H), 1.78 (m, 4H),
1.69 (m, 2H), 1.24 (d, J = 6.9 Hz, 6H), 1.23 (d, J = 6.9 Hz,
6H) ppm. 13C{1H} NMR (126 MHz, CDCl3): δ 154.3, 147.2,
145.6, 132.6, 128.2, 123.3, 123.2, 123.1, 45.1, 42.7, 38.7,
37.3, 36.7, 34.1, 32.5, 29.7, 29.2, 24.0, 23.9 ppm. HRMS
(APCI, quadrupole-orbitrap) m/z: [M]+ calculated for C24H32:
320.2499, found: 320.2493.
̈
̈
(4) Cindro, N.; Halasz, I.; Mlinaric-Majerski, K.; Basaric, N.
Photoinduced H-Abstraction in Homo- and
Protoadamantylphthalimide Derivatives in Solution and in
Organized and Constrained Media. European J. Org. Chem. 2013,
929–938.
(5) Chen, C. The Past, Present, and Future of the Yang Reaction.
Org. Biomol. Chem. 2016, 14, 8641–8647.
1
cis-ACB-4: H NMR (500 MHz, CDCl3): δ 7.17 (d, J =
(6) Gudmundsdottir, A. D.; Lewis, T. J.; Randall, L. H.; Scheffer,
J. R.; Rettig, S. J.; Trotter, J.; Wu, C. H. Geometric Requirements
for Hydrogen Abstractability and 1,4-Biradical Reactivity in the
Norrish/Yang Type II Reaction: Studies Based on the Solid State
Photochemistry and X-Ray Crystallography of Medium-Sized Ring
and Macrocyclic Diketones. J. Am. Chem. Soc. 1996, 118, 6167–
6184.
(7) Kuzmanich, G.; Vogelsberg, C. S.; Maverick, E. F.; Netto-
Ferreira, J. C.; Scaiano, J. C.; Garcia-Garibay, M. A. Reaction
Mechanism in Crystalline Solids: Kinetics and Conformational
Dynamics of the Norrish Type II Biradicals from α-Adamantyl- p -
Methoxyacetophenone. J. Am. Chem. Soc. 2012, 134, 1115–1123.
(8) Olah, G. A.; Carlson, C. G.; Lapierre, J. C. Friedel-Crafts
Isomerization. X. Aluminum Chloride Catalyzed Isomerization of
the Di-t-Butylbenzenes. J. Org. Chem. 1964, 29, 2687–2689.
(9) Ihmels, H.; Scheffer, J. R. The Norrish Type II Reaction in
the Crystalline State: Toward a Better Understanding of the
1.9 Hz, 1H), 7.15 (d, J = 7.9 Hz, 1H), 7.00 (dd, J = 7.9, 1.9
Hz, 1H), 3.37 (sept, J = 6.9 Hz, 1H), 2.93 (m, 1H), 2.88
(sept, J = 6.9 Hz, 1H), 2.49 (s, 1H), 2.38 (br s, 1H), 2.33 (d,
J = 11.1 Hz, 1H), 2.29 (d, J = 11.1 Hz, 1H), 2.20 (m, 1H),
2.02 (m, 2H), 1.82 (m, 2H), 1.73 (m, 6H), 1.67 (br s, 1H),
1.25 (d, J = 6.9 Hz, 6H), 1.21 (d, J = 6.9 Hz, 6H) ppm.
13C{1H} NMR (126 MHz, CDCl3): δ 148.2, 147.5, 142.9,
125.7, 125.1, 123.2, 85.1, 54.9, 49.9, 45.5, 41.0, 39.6, 38.1,
34.4, 33.9, 32.2, 30.9, 30.6, 28.7, 28.5, 24.7, 24.5, 24.02,
23.99 ppm. HRMS (APCI, quadrupole-orbitrap) m/z:
[M+H]+ calculated for C24H35O: 339.2682, found: 339.2693.
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