Subscribe to RSS
DOI: 10.1055/s-2002-34386
Oxabicyclo[3.2.1]oct-6-enes as Templates for the Stereoselective Synthesis of Polypropionates: Total Synthesis of Callystatin A and C19-epi-Callystatin A
Publication History
Publication Date:
26 September 2002 (online)
![](https://www.thieme-connect.de/media/synthesis/200214SpecialIssue/lookinside/thumbnails/10.1055-s-2002-34386-1.jpg)
Abstract
The total synthesis of the polyketide natural product callystatin A and its novel analog C19-epi-callystatin A is described. Our strategy features the use of an enantiomerically pure oxabicyclo[3.2.1]oct-6-ene as a template for the stereocontrolled preparation of the C15-C21 polypropionate region.
Key words
total synthesis - natural products - asymmetric synthesis - ring opening - stereoselectivity
- 1
Kobayashi M.Higuchi K.Murakami N.Tajima H.Aoki S. Tetrahedron Lett. 1997, 38: 2859 - 2
Murakami N.Wang W.Aoki M.Tsitsui Y.Higuchi K.Aoki S.Kobayashi M. Tetrahedron Lett. 1997, 38: 5533 - 3
Hayakawa Y.Sohda K.Shin-ya K.Seto H. J. Antibiotics 1995, 48: 954 - 4
Komiyama K.Okada K.Oka H.Tomisaka S.Miyano T.Funayama S.Umezawa I. J. Antibiotics 1985, 38: 220 - 5
Hayakawa Y.Sohda K.Seto H. J. Antibiotics 1996, 49: 980 - 6
Hamamoto T.Seto H.Beppu T. J. Antibiotics 1983, 36: 646 - 7
Abe K.Yoshida M.Naoki H.Horinouchi S.Beppu T. J. Antibiotics 1993, 46: 735 - 8
Murakami N.Wang W.Aoki M.Tsitsui Y.Sugimoto M.Kobayashi M. Tetrahedron Lett. 1998, 39: 2349 - 9
Crimmins MT.King BW. J. Am. Chem. Soc. 1998, 120: 9084 - 10
Smith AB.Brandt BM. Org. Lett. 2001, 3: 1685 - 11
Kalesse M.Quitschalle M.Khandavalli CP.Saeed A. Org. Lett. 2001, 3: 3107 -
12a
Marshall JA.Bourbeau MP. J. Org. Chem. 2002, 67: 2751 -
12b
Marshall JA.Schaaf GM. J. Org. Chem. 2001, 66: 7825 -
12c
Marshall JA.Fitzgerald RN. J. Org. Chem. 1999, 64: 4477 - 13
Vicario JL.Job A.Wolberg M.Muller M.Enders D. Org. Lett. 2002, 4: 1023 -
14a
Murakami N.Sugimoto M.Kobayashi M. Bioorg. Med. Chem. 2001, 9: 57 -
14b
Murakami N.Sugimoto M.Nakajima T.Kawanishi M.Tsutsui Y.Kobayashi M. Bioorg. Med. Chem. 2000, 8: 2651 - 15
Kudo N.Matsumori N.Taoka H.Fujiwara D.Schreiner EP.Wolff B.Yoshida M.Horinouchi S. Proc. Natl. Acad. Sci. U.S.A. 1999, 96: 9112 - 16
Tamura R.Saegusa K.Kakihana M.Oda D. J. Org. Chem. 1988, 53: 2723 - 17
Lautens M.de Frutos O.Stammers TA. Tetrahedron Lett. 1999, 40: 9028 - 18
Lautens M.Aspiotis R.Colucci J. J. Am. Chem. Soc. 1996, 118: 10930 -
19a
Lautens M.Chiu P. Tetrahedron Lett. 1993, 34: 773 -
19b
Lautens M.Chiu P.Colucci JT. Angew. Chem., Int. Ed. Eng. 1993, 32: 281 -
19c
Lautens M.Belter RK. Tetrahedron Lett. 1992, 33: 2617 -
19d
Lautens M.Abd-El-Aziz A.Lough A. J. Org. Chem. 1990, 55: 5305 - For the use [2.2.1]oxabicycles as templates for polypropionate tetrads, see:
-
20a
Arjona O.Menchaca R.Plumet J. J. Org. Chem. 2001, 66: 2400 -
20b
Arjona O.Menchaca R.Plumet J. Tetrahedron 2001, 57: 6751 -
20c
Arjona O.Menchaca R.Plumet J. Tetrahedron Lett. 1998, 39: 6753 -
20d
Acena JL.Arjona O.Leon M.Plumet J. Tetrahedron Lett. 1996, 37: 8957 -
21a
Vogel P.Cossy J.Plumet P.Arjona O. Tetrahedron 1999, 55: 13521 -
21b
Lautens M.Chiu P. Top. Curr. Chem. 1997, 190: 3 -
21c
Lautens M. Synlett 1993, 177 -
22a
Vakalopoulos A.Lampe TFJ.Hoffmann HMR. Org. Lett. 2001, 3: 929 -
22b
Vakalopoulos A.Hoffmann HMR. Org. Lett. 2001, 3: 177 -
22c
Misske AM.Hoffmann HMR. Tetrahedron 1999, 55: 4315 -
22d
Beck H.Hoffmann HMR. Eur. J. Org. Chem. 1999, 2991 -
22e
Dunkel R.Mentzel M.Hoffmann HMR. Tetrahedron 1997, 53: 14929 -
22f
Weiss JM.Hoffmann HMR. Tetrahedron: Asymmetry 1997, 8: 3913 -
22g
Lautens M.Ma S. Tetrahedron Lett. 1996, 37: 1727 -
22h
Yadav JS.Rao CS.Chandrasekhar S.Rama Rao AV. Tetrahedron Lett. 1995, 36: 7717 -
23a
Hunt KW.Grieco PA. Org. Lett. 2001, 4: 245 -
23b
Kim H.Hoffmann HMR. Eur. J. Org. Chem. 2000, 2195 -
23c
Nowakowski M.Hoffmann HMR. Tetrahedron Lett. 1997, 38: 1001 -
24a
Lampe TFJ.Hoffmann HMR. Tetrahedron Lett. 1996, 37: 7695 -
24b
Lampe TFJ.Hoffmann HMR.Bornscheuer UT. Tetrahedron: Asymmetry 1996, 7: 2889 - 25
Davies HML.Ahmed G.Churchhill MR. J. Am. Chem. Soc. 1996, 118: 10774 -
26a
Stark CBW.Pierau S.Wartchow R.Hoffmann HMR. Chem.-Eur. J. 2000, 6: 684 -
26b
Stark CBW.Eggert U.Hoffmann HMR. Angew. Chem. Int. Ed. 1998, 37: 1266 -
27a
Lautens M.Rovis T. J. Am. Chem. Soc. 1997, 119: 11090 -
27b
Lautens M.Chiu P.Ma S.Rovis T. J. Am. Chem. Soc. 1995, 117: 532 -
28a
Lautens M.Dockendorff C.Fagnou K.Malicki A. Org. Lett. 2002, 4: 1311 -
28b
Lautens M.Hiebert S.Renaud J.-L. J. Am. Chem. Soc. 2001, 123: 6834 -
28c
Lautens M.Hiebert S.Renaud J.-L. Org. Lett. 2000, 2: 1971 -
28d
Lautens M.Hiebert S.Renaud J.-L. J. Am. Chem. Soc. 2000, 122: 1804 -
29a
Kametani T.Tsubuki M.Tatsuzaki Y.Honda T. J. Chem. Soc., Perkin Trans. 1 1990, 639 -
29b
Kusakabe M.Kitano Y.Kobayashi Y.Sato F. J. Org. Chem. 1989, 54: 2085 - 30
Ashcroft MR.Hoffmann HMR. Org. Synth. 1978, 58: 17 - For reviews on [4 + 3] cycloadditions reactions, see:
-
31a
Hosomi A.Tominaga Y. [4 + 3] Cycloaddtions, In Comprehensive Organic Synthesis Vol. 5:Trost BM.Fleming I. Pergamon; Oxford: 1991. Chapter 5.1. p.593 -
31b
Mann J. Tetrahedron 1986, 42: 4611 -
31c
Hoffmann HMR. Angew. Chem., Int. Ed. Engl. 1984, 23: 1 -
31d
Noyori R.Hayakawa Y. Org. React. 1983, 29: 163 -
32a
Hayashi H.Nakanishi K.Brandon C.Marmur J. J. Am. Chem. Soc. 1973, 95: 8749 -
32b
McCarthy PA. Tetrahedron Lett. 1982, 23: 4199 -
32c
Meyers AI.Lawson JP. Tetrahedron Lett. 1982, 23: 4883 -
32d
Williams DR.Sit S.-Y. J. Am. Chem. Soc. 1984, 106: 2949 -
32e
Masamune S.Ma P.Okumoto H.Ellingboe JW.Ito Y. J. Org. Chem. 1984, 49: 2837 -
32f
Lavalee P.Ruel R.Grenier L.Bissonnette M. Tetrahedron Lett. 1986, 27: 679 - 33
Suffert J.Abraham E.Raeppel S.Bruecker R. Liebigs Ann. Chem. 1996, 447 - 34
Takano S.Akiyama M.Sato S.Ogasawara K. Chem. Lett. 1983, 1593 -
35a
Dias LC.Meira PRR. Tetrahedron Lett. 2002, 43: 1593 -
35b
Dias LC.Meira PRR. Tetrahedron Lett. 2002, 43: 185 - 38
Mancuso AJ.Huang S.-L.Swern D. J. Org. Chem. 1978, 43: 2480 - 39
Harada T.Kurokawa Y.Kagamihara Y.Tanaka S.Inoue A.Oku A. J. Org. Chem. 1992, 57: 1412 - There are relatively few examples of the selective oxidation of a primary alcohol in the presence of a secondary alcohol. For examples, see:
-
40a
De Luca L.Giacomelli G.Porcheddu A. Org. Lett. 2001, 3: 3041 -
40b
Einhorn J.Einhorn C.Ratajczak F.Pierre J.-L. J. Org. Chem. 1996, 61: 7452 -
40c
Nakano T.Terada T.Ishii Y.Ogawa M. Synthesis 1986, 774 -
40d
Tomioka H.Takai K.Oshima K.Nozaki H. Tetrahedron Lett. 1981, 22: 1605 -
40e
Lansbury PT.Hangauer DG.Vacca JP. J. Am. Chem. Soc. 1980, 102: 3964 -
40f
Ketchmer RA.Thompson WJ. J. Am. Chem. Soc. 1976, 98: 3379 -
40g
Fried J.Sih JC. Tetrahedron Lett. 1973, 14: 3899 - 41
Griffith WP.Ley SV. Aldrichchimica Acta 1990, 23: 13 - 42
Oizumi M.Takahashi M.Ogasawara K. Synlett 1997, 1111 - 43
Yamaguchi M.Hirao I. Tetrahedron Lett. 1983, 24: 391 - 45
Boger DL.Ichikawa S.Zhong W. J. Am. Chem. Soc. 2001, 123: 4161 - 46
Quitschalle M.Christman M.Bhatt U.Kalesse M. Tetrahedron Lett. 2001, 42: 1263 -
48a
Overman LE.Robinson LA.Zablocki J. J. Am. Chem. Soc. 1992, 114: 368 -
48b
Bender SL. PhD Thesis Harvard University; USA: 1986. -
49a
Christman M.Bhatt U.Quitschalle M.Claus E.Kalesse M. Angew. Chem. Int. Ed. 2000, 39: 4364 -
49b
Bhatt U.Christman M.Quitschalle M.Claus E.Kalesse M. J. Org. Chem. 2001, 66: 1885 - 50
Still WC.Gennari C. Tetrahedron Lett. 1983, 24: 4405 - 51
Dess DB.Martin JC. J. Org. Chem. 1983, 48: 4155
References
We independently found the same solution to the olefination problem of intermediate 25/B as was reported recently in the literature. [12a] [35]
37Alternatively, diol 27 could also be prepared from intermediate 19 (Scheme [19] ).
44(E)-Enal (Scheme [20] ) was consistently isolated from the MnO2 allylic oxidation in approximately 4% yield. This material could be recycled by stirring in 2-propanol and PPTS, forming 38 in modest yield.
47Ratio determined by comparing isolated yields and tert-butyl signals on the 1H NMR spectra of the mixed fractions of mono-silylated products. An accurate measurement of the ratio could not be based on the crude 1H NMR.