Journal of the American Chemical Society
Page 10 of 12
Accessing Polycyclic Cyclopropanes. Adv. Synth. Catal. 2020, 362,
242-247.
10 Shu, C.; Mega, R. S.; Andreassen, B. J.; Noble, A.; Aggarwal, V.
K. Synthesis of Functionalized Cyclopropanes from Carboxylic Acids
by a Radical Addition-Polar Cyclization Cascade. Angew. Chem. Int.
Ed. 2018, 57, 15430–15434.
clusters and XSEDE (CHE160082 and CHE160053). Financial
1
2
3
4
5
6
7
8
support was provided to U.K.T. and B.X. by W. W. Caruth, Jr.
Endowed Scholarship, Welch Foundation (I-1748), National
Institutes of Health (R01GM102604), American Chemical Society
Petroleum Research Fund (59177-ND1), Teva Pharmaceuticals
Marc A. Goshko Memorial Grant (60011-TEV), and Sloan
Research Fellowship. L.T.-G. is a Postdoctoral researcher of the
Fonds de la Recherche Scientifique – FNRS. L.T.-G. acknowledges
Gerald J. Meyer for granting access to his equipment to complete
the time-resolved experiments. We acknowledge Dr. Vincent
Lynch (Manager of the X-ray Diffraction Lab at UT Austin) for the
X-ray structural analysis.
1 (a) Guo, T.; Zhang, L.; Liu, X.; Fang, Y.; Jin, X.; Yang, Y.; Li,
Y.; Chen, B.; Ouyang, M., Visible-Light-Promoted Redox-Neutral
Cyclopropanation Reactions of α-Substituted Vinylphosphonates and
Other Michael Acceptors with Chloromethyl Silicate as Methylene
Transfer Reagent. Adv. Synth. Catal. 2018, 360, 4459-4463. (b) Li, P.;
Zhao, J.; Shi, L.; Wang, J.; Shi, X.; Li, F., Iodine-catalyzed diazo
activation to access radical reactivity. Nat. Commun. 2018, 9, 1972. (c)
Sayes, M.; Benoit, G.; Charette, A. B., Borocyclopropanation of
Styrenes Mediated by UV-light Under Continuous Flow Conditions.
Angew. Chem. Int. Ed. 2018, 57, 13514-13518. (d) Luo, W.; Yang, Y.;
Fang, Y.; Zhang, X.; Jin, X.; Zhao, G.; Zhang, L.; Li, Y.; Zhou, W.;
Xia, T.; Chen, B., Photoredox-Catalyzed Cyclopropanation of 1,1-
Disubstituted Alkenes via Radical-Polar Crossover Process. Adv.
Synth. Catal. 2019, 361, 4215-4221. (e) Ohtani, T.; Tsuchiya, Y.;
Uraguchi, D.; Ooi, T., Photocatalytic borylcyclopropanation of α-boryl
styrenes. Org. Chem. Front. 2019, 6, 1734-1737.
9
10
11
12
13
14
15
16
17
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
REFERENCES
(a) McGrath, N. A.; Brichacek, M.; Njardarson, J. T. A Graphical
Journey of Innovative Organic Architectures That Have Improved Our
Lives. J. Chem. Ed. 2010, 87, 1348-1349. (b) Wessjohann, L. A.;
Brandt, W.; Thiemann, T. Biosynthesis and Metabolism of
Cyclopropane Rings in Natural Compounds. Chem. Rev. 2003, 103,
1625−1648.
2 (a) Talele, T. T. The “Cyclopropyl Fragment” is a Versatile Player
that Frequently Appears in Preclinical/Clinical Drug Molecules. J. Med.
Chem. 2016, 59, 8712−8756. (d) Chen, D. Y.-K.; Pouwer, R. H.;
Richard, J.-A. Recent advances in the total synthesis of cyclopropane-
containing natural products. Chem. Soc. Rev. 2012, 41, 4631−4642.
3 (a) Dill, J. D.; Greenberg, A.; Liebman, J. F. Substituent effects on
strain energies. J. Am. Chem. Soc. 1979, 101, 6814−6826. (b) de
Meijere, A. Bonding Properties of Cyclopropane and Their Chemical
Consequences. Angew. Chem., Int. Ed. 1979, 18, 809−886.
2 De Mayo, P.; Editor, Organic Chemistry, Vol. 42: Rearrangements
in Ground and Excited States, Vol. 1-3. Academic Press: 1980.
13 (a) Singh, K.; Staig, S. J.; Weaver, J. D. Facile Synthesis of Z‐
Alkenes via Uphill Catalysis. J. Am. Chem. Soc. 2014, 136,
5275‒5278. Zheng, C.; Wan-Min, C.;, Li, H-L.; Na, R.-S.; Shang,
R. Cis-Selective Decarboxylative Alkenylation of Aliphatic
Carboxylic
Acids
with
Vinyl
Arenes
Enabled
by
Photoredox/Palladium/Uphill Triple. Org. Lett. 2018, 20, 2559-2563.
(c) Metternich, J. B.; Gilmour, R., A Bio-Inspired, Catalytic E → Z
Isomerization of Activated Olefins. J. Am. Chem. Soc. 2015, 137,
11254-11257. (d) Metternich, J. B.; Artiukhin, D. G.; Holland, M. C.;
von Bremen-Kühne, M.; Neugebauer, J.; Gilmour, R., Photocatalytic
E → Z Isomerization of Polarized Alkenes Inspired by the Visual
Cycle: Mechanistic Dichotomy and Origin of Selectivity. J. Org.
Chem. 2017, 82, 9955-9977. (e) Pearson, C. M.; Snaddon, T. N.,
Alkene Photo-Isomerization Inspired by Vision. ACS Cent. Sci. 2017,
3, 922-924. (f) Litman, Z. C.; Wang, Y.; Zhao, H.; Hartwig, J. F.,
Cooperative asymmetric reactions combining photocatalysis and
enzymatic catalysis. Nature 2018, 560, 355-359. (g) Molloy, J. J.;
Metternich, J. B.; Daniliuc, C. G.; Watson, A. J. B.; Gilmour, R.,
Contra-Thermodynamic, Photocatalytic E→Z Isomerization of
Styrenyl Boron Species: Vectors to Facilitate Exploration of Two-
Dimensional Chemical Space. Angew. Chem. Int. Ed. 2018, 57, 3168-
3172. (h) Faßbender, S. I.; Molloy, J. J.; Mück-Lichtenfeld, C.;
Gilmour, R., Geometric E→Z Isomerisation of Alkenyl Silanes by
Selective Energy Transfer Catalysis: Stereodivergent Synthesis of
Triarylethylenes via a Formal anti-Metallometallation. Angew. Chem.
Int. Ed. 2019, 58, 18619-18626. (i) Livingstone, K.; Tenberge, M.;
Pape, F.; Daniliuc, C. G.; Jamieson, C.; Gilmour, R., Photocatalytic E
→ Z Isomerization of β-Ionyl Derivatives. Org. Lett. 2019, 21, 9677-
9680. (j) Meng, Q.-Y.; Schirmer, T. E.; Katou, K.; König, B.,
Controllable Isomerization of Alkenes by Dual Visible-Light-Cobalt
Catalysis. Angew. Chem. Int. Ed. 2019, 58, 5723-5728. (k) Naskar, S.;
Roy Chowdhury, S.; Mondal, S.; Maiti, D. K.; Mishra, S.; Das, I.,
Visible-Light-Activated Divergent Reactivity of Dienones:
4
(a) Wong, H. N. C.; Hon, M.-Y.; Tse, C.-W.; Yip, Y.-C.; Tanko,
J.; Hudlicky, T. Use of Cyclopropanes and Their Derivatives in
Organic Synthesis. Chem. Rev. 1989, 89, 165−198. (b) Carbocyclic
Three-Membered Ring Compounds: Cyclopropanes, Transformations;
Houblen-Weyl Methods of Organic Chemistry, Vol. E17c; Thieme:
Stuttgart, Germany, 1997; (c) Carson, C. A.; Kerr, M. A. Heterocycles
from Cyclopropanes: Applications in Natural Product Synthesis. Chem.
Soc. Rev. 2009, 38, 3051−3060. (d) Ebner, C.; Carreira, E. M.
Cyclopropanation Strategies in Recent Total Syntheses. Chem. Rev.
2017, 117, 11651−11679.
5
(a) Simmons, H. E.; Smith, R. D. A New Synthesis of
Cyclopropanes from Olefins. J. Am. Chem. Soc. 1958, 80, 5323−5324.
(b) Simmons, H. E.; Smith, R. D. A New Synthesis of Cyclopropanes.
J. Am. Chem. Soc. 1959, 81, 4256−4264. (c) (a) Simmons, H. E.; Cairns,
T. L.; Vladuchick, S. A.; Hoiness, C. M. Cyclopropanes from
Unsaturated Compounds, Methylene Iodide, and Zinc‐Copper Couple.
Org. React. 1973, 20, 1-131.
6
(a) Doyle, M. P.; McKervey, M. A.; Ye, T. Modern Catalytic
Methods for Organic Synthesis with Diazo Compounds:
From Cyclopropanes to Ylides; Wiley-Interscience: New York,
1998. (b) Davies, H. M. L. Eur. J. Org. Chem. 1999, 2459-2469.
7 Patai, S.; Rappoport, Z. The Chemistry of the Cyclopropyl Group,
Chapter 9; Wiley & Sons: New York, 1987.
8
(a) delꢀHoyo, A. M.; Herraiz, A. G.; Suero, M. G.
A
“Stereoconvergent Cyclopropanation Reaction of Styrenes.” Angew.
Chem. Int. Ed. 2017, 56, 1610–1613. (b) del Hoyo, A. M.; Suero, M.
G. “Photoredox-Catalyzed Cyclopropanation of Michael Acceptors.”
Eur. J. Org. Chem. 2017, 2017, 2122–2125. (c) Herraiz, A. G.; Suero,
M. G. New Alkene Cyclopropanation Reactions Enabled by
Photoredox Catalysis via Radical Carbenoids. Synthesis 2019, 51,
2821-2828. (d) Herraiz, A. G.; Suero, M. G., A transition-metal-free &
diazo-free styrene cyclopropanation. Chem. Sci. 2019, 10, 9374-9379.
9 (a) Phelan, J. P.; Lang, S. B.; Compton, J. S.; Kelly, C. B.; Dykstra,
R.; Gutierrez, O.; Molander, G. A. “ Redox-Neutral Photocatalytic
Cyclopropanation via Radical/Polar Crossover.“ J. Am. Chem.
Soc. 2018, 140, 8037-8047. (b) Milligan, J. A.; Phelan, J. P.; Polites,
C. C.; Kelly, C. B.; Molander, G. A. “Radical/Polar Annulation
Reactions (RPARs) Enable the Modular Construction of
Cyclopropanes.” Org. Let. 2018, 20, 6840-6844. (c) Milligan, J. A.;
Burns, K. L.; Le, A. V.; Polites, V. C.; Wang, Z.-J.; Molander, G.
A.; Kelly, C. B., Radical-Polar Crossover Annulation: A Platform for
Dimerization in Neat Conditions and Regioselective
E to Z
Isomerization in the Solvent. Org. Lett. 2019, 21, 1578-1582.
4 Ota, E.; Wang, H.; Frye, N. L.; Knowles, R. R. A Redox Strategy
for Light-Driven, Out-of-Equilibrium Isomerizations and Application
to Catalytic C−C Bond Cleavage Reactions. J. Am. Chem. Soc. 2019,
141, 1457–1462.
5
(a) Cristol, S. J.; Lee, G. A. Photochemical Transformations. V.
Allylic Rearrangements and Rearrangement of Allylic Halides to
Cyclopropyl Halides. J. Am. Chem. Soc. 1969, 91, 7554‒7555. (b)
Cristol, S. J.; Lee, G. A.; Noreen, A. L. Photochemical transformations.
VIII. Photosensitized Rearrangements of Some Acyclic Allylic Halides.
J. Am. Chem. Soc. 1973, 95, 7067‒7074. (c) Cristol, S. J.; Micheli, R.
P. Photochemical Transformations. XI. Photochemical and Thermal
Rearrangements of Some beta-Substituted Allylic Systems. J. Org.
ACS Paragon Plus Environment