Chemistry - A European Journal
10.1002/chem.202001548
COMMUNICATION
In addition, this mechanistic scenario can explain the Acknowledgments
predominant formation of the regioisomers 3’b when electron-
This research was supported by the European Research Council
ERC Consolidator Grant “GAINBYSTRAIN” to D.B.W).
donating arene units are attached to the carbene (Scheme 2). A
more electron-rich arene unit leads to a higher nucleophilicity of
the adjacent carbonyl moiety, which is a prerequisite for the
formation of oxirene-type intermediates. Further evidence for
oxirene formation in the case of furan backbones is given by the
generation of diols 6a and 6b, which are traced back to an
intermolecularly formed and concomitantly hydrolyzed epoxide 4
(
Conflict of interest
The authors declare no conflict of interest.
Keywords: annulation • cycloaddition • carbonyl ylides •
carbenes • catalysis
(
Figure 2). Further mechanistic evidence for the crucial role of
Lewis and Brønsted acid participation is provided by oligomers 7
which were isolated in moderate yield (Figure 2) when the
reaction was conducted in the absence of those acids. These
oligomers are the products of an initial (3+2)-cycloaddition of
oxirene C with carbonyl ylide A, followed by further (3+2)-
cycloaddition reactions of the respective carbonyl moiety with
ylide A.
[
1]
a) W. Kirmse, Eur. J. Org. Chem. 2002, 2193; b) H. Wynberg, Chem. Rev.
960, 60, 169.
1
[2]
a) A. Ford, H. Miel, A. Ring, C. N. Slattery, A. R. Maguire, M. A. McKervey,
Chem. Rev. 2015, 115, 9981; b) T. Ye, M. A. McKervey, Chem. Rev. 1994,
94, 1091; c) M. P. Doyle, D. C. Forbes, Chem. Rev. 1998, 98, 911; d) H.
M. L. Davies, J. S. Alford, Chem. Soc. Rev. 2014, 43, 5151; e) Q.-Q.
Cheng, Y. Deng, M. Lankelma, M. P. Doyle, Chem. Soc. Rev. 2017, 46,
5425.
[
3]
a) J. He, L. G. Hamann, H. M. L. Davies, R. E. J. Beckwith, Nat. Commun.
2015, 6, 5943; b) B. T. Parr, H. M. L. Davies, Nat. Commun. 2014, 5,
4455.
[
[
[
4]
5]
6]
J. Wu, X. Li, X. Qi, X. Duan, W. L. Cracraft, I. A. Guzei, P. Liu, W. Tang,
J. Am. Chem. Soc. 2019, 141, 19902.
a) Z. Liu, P. Sivaguru, G. Zanoni, E. A. Anderson, X. Bi, Angew. Chem.
Int. Ed. 2018, 57, 8927; Angew. Chem. 2018, 130, 9065.
a) D. Rix, R. Ballesteros-Garrido, W. Zeghida, C. Besnard, J. Lacour,
Angew. Chem. Int. Ed. 2011, 50, 7308; Angew. Chem. 2011, 123, 7446;
b) W. Zeghida, C. Besnard, J. Lacour, Angew. Chem. Int. Ed. 2010, 49,
7253; Angew. Chem. 2010, 122, 7411; c) R. Ballesteros-Garrido, D. Rix,
C. Besnard, J. Lacour, Chem. Eur. J. 2012, 18, 6626.
[
[
7]
8]
a) D. P. Hari, L. Schouwey, V. Barber, R. Scopelliti, F. Fadaei-Tirani, J.
Waser, Chem. Eur. J. 2019, 25, 9522; b) D. P. Hari, J. Waser, J. Am.
Chem. Soc. 2016, 138, 2190.
a) S. Jana, R. M. Koenigs, Org. Lett. 2019, 21, 3653; b) F. He, C. Pei, R.
M. Koenigs, Chem. Commun. 2020, 56, 599; c) R. Hommelsheim, Y. Guo,
Z. Yang, C. Empel, R. M. Koenigs, Angew. Chem. Int. Ed. 2019, 58, 1203;
Angew. Chem. 2019, 131, 1216.
[
[
9]
a) A. Suneja, C. Schneider, Org. Lett. 2018, 20, 7576; b) J. Kalepu, S.
Katukojvala, Angew. Chem. Int. Ed. 2016, 55, 7831; Angew. Chem. 2016,
128, 7962 c) V. Kanchupalli, S. Katukojvala, Angew. Chem. Int. Ed. 2018,
7, 5433; Angew. Chem. 2018, 130, 5531.
5
10] a) A. Padwa, D. C. Dean, L. Zhi, J. Am. Chem. Soc. 1992, 114, 593; b)
A. Padwa, J. M. Kassir, M. A. Semones, M. D. Weingarten, J. Org. Chem.
1
995, 60, 53; c) A. Padwa, Helv. Chim. Acta 2005, 88, 1357; d) A. Padwa,
J. M. Kassir, M. A. Semones, M.D. Weingarten, Tetrahedron Lett. 1993,
4, 7853; d) R. Huisgen, Angew. Chem. Int. Ed. Engl. 1977, 16, 572;
Angew. Chem. 1977, 89, 589.
3
Figure 2. A: Isolated hydrolyzed intermediates of furan substrates. B: Oligomers
observed in the absence of Lewis and Brønsted acid.[a] Compound 6a was
isolated as a by-product in the formation of 3g.
[11] a) T. Hashimoto, K. Maruoka, Chem. Rev. 2015, 115, 5366; b) Y. Deng,
L. A. Massey, Y. A. Rodriguez Núñez, H. Arman, M. P. Doyle, Angew.
Chem. Int. Ed. 2017, 56, 12292; Angew. Chem. 2017, 129, 12460; c) Y.
Fegheh-Hassanpour, T. Arif, H. O. Sintim, H. H. al Mamari, D. M.
Hodgson, Org. Lett. 2017, 19, 3540; d) H. Suga, Y. Sekikawa, S. Misawa,
D. Kinugawa, R. Oda, K. Itoh, Y. Toda, R. Kiyono, J. Org. Chem. 2015,
In conclusion, we have discovered an unprecedented
dimerization cascade that transforms, via cooperative Rh(II),
Lewis and Brønsted acid catalysis, a simple diazo carbonyl
compound into oxygen-rich oligocyclic scaffolds. In a regio- and
diastereoselective fashion four new bonds, three different
functional groups and four contiguous stereocenters are formed
in one step. Mechanistic investigations by the isolation and X-ray
investigation of some intermediates and their subjection to
specific reaction conditions revealed a complex framework of
cycloaddition reactions also involving transient species of the
ketocarbene equilibrium and skeletal rearrangements.
80, 6687.
[12] Q.-Q. Cheng, J. Yedoyan, H. Arman, M. P. Doyle, Angew. Chem. Int. Ed.
2016, 55, 5573; Angew. Chem. 2016, 128, 5663.
[13] a) A. Suneja, H. J. Loui, C. Schneider, Angew. Chem. Int. Ed. 2020;
Angew. Chem. 2020, 27, 555; b) M. Petzold, P. G. Jones, D. B. Werz,
Angew. Chem. Int. Ed. 2019, 58, 6225; Angew. Chem. 2019, 131, 6291.
[14] a) M. Takebayashi, T. Ibata, K. Ueda, T. Ohashi, BCSJ 1970, 43, 3964;
b) K. Ueda, T. Ibata, M. Takebayashi, Bull. Chem. Soc. Jpn. 1972, 45,
2779.
[15] In contrast to the reports, our X-ray diffraction and NMR-data suggest a
structural revision of compound 2.
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