Anie 201805323
Anie 201805323
Anie 201805323
Communications Chemie
Ylides, such as carbonyl and sulfur ylides, are readily Scheme 1. Transition-metal-catalyzed reactions of a-diazoimides with
sulfur ylides and the development of enoldiazoimides.
accessible reagents (or intermediates) that have been effi-
ciently utilized in various organic transformations, especially
cycloaddition reactions.[1] Carbonyl ylides (R2C=O+@C@R2)
are conveniently formed by transition-metal-catalyzed intra- cyclopropanation, epoxidation, aziridination, and other [n +
or intermolecular reactions of carbonyls (R2C=O) with diazo 1] cycloaddition processes with release of the corresponding
compounds (N2=CR2), and they are widely employed in 1,3- sulfides (R2S),[4] including a recently reported [3+ +1] cyclo-
dipolar cycloadditions as (+C@O@C@)-type dipolar compo- addition reaction with enoldiazoacetates.[5]
nents.[2] For example, 1,3-oxazolium-4-oxide derivatives (iso- Given that both carbonyl ylides and sulfur ylides have
mgnchnones), generated in situ by metal-catalyzed (espe- exhibited remarkable efficiencies in their respective cyclo-
cially rhodium) intramolecular cyclization of a-diazoimides addition reactions,[2–4] we were intrigued by the possibility
(1 a and 2 a; Scheme 1 a), have been developed for the that a combination of these two subclasses of ylides could lead
construction of a series of oxa- and aza-polycyclic ring to new cycloaddition outcomes. Therefore, reactions between
systems.[3] Sulfur ylides (R2S+@C@R2 ; e.g., 3 a, Scheme 1 a) in situ generated isomgnchnone intermediates and the sulfur
have been easily prepared from their corresponding sulfo- ylide 3 a were initially investigated, but no cross-products
nium salts (R2S+@CHR2·X@) under basic conditions, and they were obtained from the reactions initiated by dinitrogen (N2)
usually serve as one-carbon synthons (the ylide carbon) in extrusion from either the a-diazoimide 1 a or 2 a (Sche-
me 1 a).[6] Inspired by recent advances in the cycloaddition
[*] Dr. Q.-Q. Cheng,[+] L. A. Massey,[+] B. S. Willett, Dr. Y. Deng, reactions of enoldiazo compounds,[7] especially by those
Dr. H. Arman, Prof. Dr. M. P. Doyle studies in which novel reactivities were achieved,[8] we
Department of Chemistry, The University of Texas at San Antonio constructed enoldiazoimides, a new subclass of enoldiazo
One UTSA Circle, San Antonio, TX 78249 (USA)
compounds, by a simple silyl-enolization of acetyldiazoimides
E-mail: [email protected]
Homepage: http://www.utsa.edu/chem/faculty/DoyleLab/
(e.g., 2 a!4 a, Scheme 1 b).[9] To our delight, the cross-
coupled product 5 a, which is an unpredicted formal
Dr. Y. Deng
Current address: Department of Chemistry, Western Kentucky [4+
+2] cycloadduct, was obtained in 74 % yield along with
University, Bowling Green, KY 42101 (USA) methyl acetate (MeOAc) from a copper-catalyzed reaction of
[+] These authors contributed equally to this work. the enoldiazoimide 4 a with 3 a (Scheme 1 c). Notably, sub-
Supporting information and the ORCID identification number(s) for stituted indolizidinones are the core structure of numerous
the author(s) of this article can be found under: biologically active natural products and pharmaceuticals,[10]
https://doi.org/10.1002/anie.201805323. and the development of this methodology would allow
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Angewandte
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from enoldiazoimides and sulfonium salts, serving as the [4] For reviews, see: a) A.-H. Li, L.-X. Dai, V. K. Aggarwal, Chem.
initial electrophile and nucleophile, respectively. This formal Rev. 1997, 97, 2341; b) E. M. McGarrigle, E. L. Myers, O. Illa,
[4++2] cycloaddition also involves C@O bond cleavage, silyl M. A. Shaw, S. L. Riches, V. K. Aggarwal, Chem. Rev. 2007, 107,
5841; c) L.-Q. Lu, T.-R. Li, Q. Wang, W.-J. Xiao, Chem. Soc. Rev.
group migration, acetyl group migration, and C@S bond
2017, 46, 4135.
cleavage along the reaction pathway. The essential role of the [5] Y. Deng, L. A. Massey, P. Y. Zavalij, M. P. Doyle, Angew. Chem.
silyl-protected enoldiazoimide is seen in the complete Int. Ed. 2017, 56, 7479; Angew. Chem. 2017, 129, 7587.
absence of a cross-product when the corresponding acetyl- [6] Both rhodium and copper catalysts were tested in reactions of
diazoimide was employed. We hope this simple strategy either a-diazoimides 1 a or 2 a with the sulfur ylide 3 a.
(acyl!enol) will create new possibilities for further method- [7] For reviews, see: a) Q.-Q. Cheng, Y. Deng, M. Lankelma, M. P.
Doyle, Chem. Soc. Rev. 2017, 46, 5425; b) Q.-Q. Cheng, Y. Yu, J.
ology developments in the field.
Yedoyan, M. P. Doyle, ChemCatChem 2018, 10, 488.
[8] For selected examples, see: a) X. Wang, X. Xu, P. Y. Zavalij,
M. P. Doyle, J. Am. Chem. Soc. 2011, 133, 16402; b) Q.-Q. Cheng,
Acknowledgements J. Yedoyan, H. Arman, M. P. Doyle, J. Am. Chem. Soc. 2016, 138,
44; c) Q.-Q. Cheng, J. Yedoyan, H. Arman, M. P. Doyle, Angew.
Support for this research from the National Science Founda- Chem. Int. Ed. 2016, 55, 5573; Angew. Chem. 2016, 128, 5663;
tion (CHE-1464690) is gratefully acknowledged. The HRMS d) Q.-Q. Cheng, M. Lankelma, D. Wherritt, H. Arman, M. P.
Doyle, J. Am. Chem. Soc. 2017, 139, 9839; e) Y. Deng, L. A.
used in this research was supported by a grant from the
Massey, Y. A. Rodriguez NfflÇez, H. Arman, M. P. Doyle, Angew.
National Institutes of Health (G12MD007591). The National Chem. Int. Ed. 2017, 56, 12292; Angew. Chem. 2017, 129, 12460.
Science Foundation supported the acquisition of a NMR [9] For experimental details, see Section 2 of the Supporting
spectrometer used in this study (CHE-1625963). L.A. Massey Information.
acknowledges support from the National Institute of General [10] For reviews, see: a) J. F. Pizzolato, L. B. Saltz, Lancet 2003, 361,
Medical Sciences branch of the National Institutes of Health 2235; b) Y. Pommier, Nat. Rev. Cancer 2006, 6, 789; c) R. P.
(MARC-U*STAR GM07717). Verma, C. Hansch, Chem. Rev. 2009, 109, 213; d) Y. Pommier,
Chem. Rev. 2009, 109, 2894; e) Y. Pommier, C. Marchand, Nat.
Rev. Drug Discovery 2012, 11, 25.
[11] Only a trace amount of 5 a was formed after 4 a was fully
Conflict of interest consumed.
[12] CCDC 1821831 (5 d) contains the supplementary crystallo-
The authors declare no conflict of interest. graphic data for this paper. These data can be obtained free of
charge from The Cambridge Crystallographic Data Centre.
[13] a) R. Shintani, K. Takatsu, M. Takeda, T. Hayashi, Angew.
Keywords: copper · cycloaddition · diazo compounds ·
Chem. Int. Ed. 2011, 50, 8656; Angew. Chem. 2011, 123, 8815;
sulfonium salts · ylides b) S. H. Bertz, R. A. Hardin, M. D. Murphy, C. A. Ogle, J. D.
Richter, A. A. Thomas, J. Am. Chem. Soc. 2012, 134, 9557; c) W.
How to cite: Angew. Chem. Int. Ed. 2018, 57, 10343 – 10346 Xie, S. Chang, Angew. Chem. Int. Ed. 2016, 55, 1876; Angew.
Angew. Chem. 2018, 130, 10500 – 10503 Chem. 2016, 128, 1908; d) A. P. Pulis, K. Yeung, D. J. Procter,
Chem. Sci. 2017, 8, 5240.
[1] For reviews, see: a) Nitrogen, Oxygen and Sulfur Ylide Chemis- [14] a) A. Padwa, M. A. Brodney, J. P. Marino, S. M. Sheehan, J. Org.
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Applications in Ligand Design, Organic and Catalytic Trans-
formations (Ed.: V. H. Gessner), Springer, New York, 2018.
[2] For reviews, see: a) D. M. Hodgson, F. Y. T. M. Pierard, P. A.
Stupple, Chem. Soc. Rev. 2001, 30, 50; b) A. Padwa, Helv. Chim.
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Muthusamy, Org. React. 2013, 80, 133. Manuscript received: May 7, 2018
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1996, 96, 223; b) A. Padwa, Chem. Soc. Rev. 2009, 38, 3072; c) A. Accepted manuscript online: June 4, 2018
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10346 www.angewandte.org T 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim Angew. Chem. Int. Ed. 2018, 57, 10343 –10346