Generation and Rearrangement of (1-Hydroxycyclopropyl)- and (1-Hydroxycyclobutyl)carbene
Joseph D. DeAngelo
A , Sayaka Hatano B C and Dasan M. Thamattoor A C
A Department of Chemistry, Colby College, Waterville, ME 04901, USA.
B Department of Chemistry, Graduate School of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, Hiroshima 739-8526, Japan.
C Corresponding authors. Email: sa-hatano@hiroshima-u.ac.jp; dmthamat@colby.edu
Australian Journal of Chemistry 72(11) 890-893 https://doi.org/10.1071/CH19379
Submitted: 5 August 2019 Accepted: 11 September 2019 Published: 10 October 2019
Abstract
Photolysis of exo-1-(1a,9b-dihydro-1H-cyclopropa[l]phenanthren-1-yl)cyclopropan-1-ol and exo-1-(1a,9b-dihydro-1H-cyclopropa[l]phenanthren-1-yl)cyclobutan-1-ol in benzene-d6 produces (1-hydroxycyclopropyl)- and (1-hydroxycyclobutyl)carbene respectively. It was observed that (1-hydroxycyclopropyl)carbene rearranges to cyclobutanone whereas (1-hydroxycyclobutyl)carbene forms cyclopentanone. Formation of both ketones is attributed to tautomerization of the corresponding enols that arise from ring expansion of the carbenes. Products assignable to intramolecular C–H insertions were not detected in the photolysates.
References
[1] (a) L. Friedman, J. G. Berger, J. Am. Chem. Soc. 1961, 83, 500.| Crossref | GoogleScholarGoogle Scholar |
(b) W. Kirmse, B. V. Wedel, Justus Liebigs Ann. Chem. 1963, 666, 1.
| Crossref | GoogleScholarGoogle Scholar |
(c) M. J. Goldstein, W. R. Dolbier, J. Am. Chem. Soc. 1965, 87, 2293.
| Crossref | GoogleScholarGoogle Scholar |
(d) H. M. Frey, I. D. R. Stevens, J. Chem. Soc. 1965, 3101.
| Crossref | GoogleScholarGoogle Scholar |
(e) H. M. Frey, Adv. Photochem. 1966, 4, 225.
(f) K. T. Chang, H. Shechter, J. Am. Chem. Soc. 1979, 101, 5082.
| Crossref | GoogleScholarGoogle Scholar |
(g) M. Fukushima, M. Jones, U. H. Brinker, Tetrahedron Lett. 1982, 23, 3211.
| Crossref | GoogleScholarGoogle Scholar |
(h) B. M. Armstrong, M. L. McKee, P. B. Shevlin, J. Am. Chem. Soc. 1995, 117, 3685.
| Crossref | GoogleScholarGoogle Scholar |
(i) H. C. Glick, I. R. Likhovorik, M. Jones, Tetrahedron Lett. 1995, 36, 5715.
| Crossref | GoogleScholarGoogle Scholar |
[2] (a) R. Bonneau, M. T. H. Liu, in Advances in Carbene Chemistry (Ed. U. H. Brinker) 1998, Vol. 2, pp. 1–28 (JAI Press: Stamford, CT).
(b) M. S. Platz, in Advances in Carbene Chemistry (Ed. U. H. Brinker) 1998, Vol. 2, pp. 133–174 (JAI Press: Stamford, CT).
[3] D. M. Thamattoor, J. R. Snoonian, H. M. Sulzbach, C. M. Hadad, J. Org. Chem. 1999, 64, 5886.
| Crossref | GoogleScholarGoogle Scholar |
[4] R. A. Farlow, D. M. Thamattoor, R. B. Sunoj, C. M. Hadad, J. Org. Chem. 2002, 67, 3257.
| Crossref | GoogleScholarGoogle Scholar | 12003533PubMed |
[5] E. Schmitz, A. Stark, C. Hoerig, Chem. Ber. 1965, 98, 2509.
| Crossref | GoogleScholarGoogle Scholar |
[6] K. M. Morgan, M. J. O’Connor, J. L. Humphrey, K. E. Buschman, J. Org. Chem. 2001, 66, 1600.
| Crossref | GoogleScholarGoogle Scholar | 11262102PubMed |
[7] (a) N. L. Drake, T. R. Sweeney, J. Org. Chem. 1946, 11, 67.
| Crossref | GoogleScholarGoogle Scholar | 21013437PubMed |
(b) W. T. Ford, M. Newcomb, J. Am. Chem. Soc. 1973, 95, 6277.
| Crossref | GoogleScholarGoogle Scholar |
[8] O. G. Kulinkovich, S. V. Sviridov, D. A. Vasilevski, Synthesis 1991, 234.
| Crossref | GoogleScholarGoogle Scholar |
[9] J. M. Nguyen, D. M. Thamattoor, Synthesis 2007, 2093.
[10] K. S. Graves, D. M. Thamattoor, P. R. Rablen, J. Org. Chem. 2011, 76, 1584.
| Crossref | GoogleScholarGoogle Scholar | 21338136PubMed |
[11] CIF files for the two precursors have been deposited at the Cambridge Crystallographic Data Centre (CCDC). CCDC deposition numbers are 1945138 for 32 and 1945137 for 35.
[12] For a recent theoretical discussion of the structure and chemistry of cyclobutylcarbenes, see: M. G. Rosenberg, U. H. Brinker, Tetrahedron Lett. 2018, 59, 645.
| Crossref | GoogleScholarGoogle Scholar |
[13] (a) L. Friedman, H. Shechter, J. Am. Chem. Soc. 1960, 82, 1002.
| Crossref | GoogleScholarGoogle Scholar |
(b) W. W. Schoeller, J. Org. Chem. 1980, 45, 2161.
| Crossref | GoogleScholarGoogle Scholar |
