Abstract
Enzymatic dihydroxylation of β-bromoethylbenzene provided a homochiral diene diol that served as starting material for the synthesis of the complete morphinan skeleton via an intramolecular Heck cyclization.
Key words
enzymatic dihydroxylation - Heck reaction - Mitsunobu reaction - Friedel-Crafts reaction - morphinans
References and Notes
For reviews of morphine syntheses, see:
1a
Zezula J.
Hudlicky T.
Synlett
2005,
388
1b
Taber DF.
Neubert TD.
Schlecht MF. In
Strategies and Tactics in Organic Synthesis
Vol. 5:
Harmata M.
Academic Press;
Oxford:
2004.
p.353-389
1c
Blakemore PR.
White JD.
Chem. Commun.
2002,
1159
1d
Novak BH.
Hudlicky T.
Reed JW.
Mulzer J.
Trauner D.
Curr. Org. Chem.
2000,
4:
343
1e
Hudlicky T.
Butora G.
Fearnley SP.
Gum AG.
Stabile MR.
A Historical Perspective of Morphine Syntheses , In Studies in Natural Product Chemistry
Vol. 18: Atta-ur-Rahman, Ed.; Elsevier;
Amsterdam:
1996.
p.43-154
1f
Organic Synthesis Highlights II
Waldmann H.
VCH;
Weinheim:
1995.
p.407
1g
Maier M.
Organic Synthesis Highlights II
Waldmann H.
VCH;
Weinheim:
1995.
p.357-369
2a
Taber DF.
Neubert TD.
Rheingold AL.
J. Am. Chem. Soc.
2002,
124:
12416
2b
Taber DF.
Neubert TD.
Schlecht MF. In
Strategies and Tactics in Organic Synthesis
Vol. 5:
Harmata M.
Academic Press;
Oxford:
2004.
p.353-389
3a
Parker KA.
Fokas D.
J. Am. Chem. Soc.
1992,
114:
9688
3b
Parker KA.
Fokas D.
J. Org. Chem.
1994,
59:
3927
3c
Parker KA.
Fokas D.
J. Org. Chem.
1994,
59:
3933
3d
Parker KA.
Fokas D.
J. Org. Chem.
2006,
71:
449
4a
Butora G.
Hudlicky T.
Fearnley SP.
Gum AG.
Stabile MR.
Abboud KA.
Tetrahedron Lett.
1996,
37:
8155
4b
Butora G.
Hudlicky T.
Fearnley SP.
Stabile MR.
Gum AG.
Gonzalez D.
Synthesis
1998,
665
5a
Hong CY.
Kado N.
Overman LE.
J. Am. Chem. Soc.
1993,
115:
11028
5b
Heerding DA.
Hong CY.
Kado N.
Look GC.
Overman LE.
J. Org. Chem.
1993,
58:
6947
6a
Trost BM.
Tang W.
J. Am. Chem. Soc.
2002,
124:
14542
6b
Trost BM.
Toste FD.
J. Am. Chem. Soc.
2000,
122:
11262
6c
Trost BM.
Tang W.
Angew. Chem. Int. Ed.
2002,
41:
2795
6d
Trost BM.
Tang W.
Toste FD.
J. Am. Chem. Soc.
2005,
127:
14785
7
Liou J.-P.
Cheng C.-Y.
Tetrahedron Lett.
2000,
41:
915
8
Hsin L.-W.
Chang L.-T.
Chen C.-W.
Hsu C.-H.
Chen H.-W.
Tetrahedron
2005,
61:
513
9a
Frey DA.
Duan C.
Hudlicky T.
Org. Lett.
1999,
1:
2085
9b
Frey DA.
Duan C.
Ghiviriga I.
Hudlicky T.
Coll. Czech. Chem. Commun.
2000,
65:
561
10
Botari P.
Endoma MA.
Hudlicky T.
Ghiviriga I.
Abboud KA.
Coll. Czech. Chem. Commun.
1999,
64:
203
11
Stabile MR.
Hudlicky T.
Meisels ML.
Tetrahedron: Asymmetry
1995,
6:
537
12 For synthesis of octahydroisoquinolines by electrochemical cyclizations, see: Endoma MA.
Butora G.
Claeboe CD.
Hudlicky T.
Tetrahedron Lett.
1997,
38:
8833
13 For the conversion of 5 into 15 , see: Zezula J.
PhD Thesis
University of Florida;
USA:
2003.
14
Ghosh S.
Kinney WA.
Gauthier DA.
Lawson EC.
Hudlicky T.
Maryanoff BE.
Can. J. Chem.
2006,
84:
555
15
Okuda S.
Yamaguchi S.
Tsuda K.
Chem. Pharm. Bull.
1965,
13:
1092
16a
Evans DA.
Mitch CH.
Tetrahedron Lett.
1982,
23:
285
16b
Evans DA.
Mitch CH.
Thomas RC.
Zimmerman DM.
Robey RL.
J. Am. Chem. Soc.
1980,
102:
5955
17
Schultz AG.
Lucci RD.
Napier JJ.
Kinoshita H.
Ravichandran R.
Shannon P.
Yee YK.
J. Org. Chem.
1985,
50:
217
18
Nagata H.
Miyazawa N.
Ogasawara K.
Chem. Commun.
2001,
1094
19 For the description of model studies see ref. 1a.
20a
Rapoport H.
Stevenson GH.
J. Am. Chem. Soc.
1954,
76:
1796
20b
Rapoport H.
Nauman R.
Bissell ER.
Bonner RM.
J. Org. Chem.
1950,
15:
1103
20c Stereochemistry of C-10 hydroxyl: Rapoport H.
Masamune S.
J. Am. Chem. Soc.
1955,
77:
4330
21
Barber RB.
Rapoport H.
J. Med. Chem.
1976,
19:
1175
22
Wunderly SW.
Brochmann-Hanssen E.
J. Org. Chem.
1977,
42:
4277
23
Takeda M.
Inoue H.
Kugita H.
Tetrahedron
1969,
25:
1839
24a
Kugita H.
Takeda M.
Inoue H.
Tetrahedron
1969,
25:
1851
24b
Kugita H.
Takeda M.
Inoue H.
J. Med. Chem.
1970,
13:
973
25 It is likely that the hydrogenation of neopine-type compounds only proceeds to the natural configuration at C-14 in systems containing the full phenanthrene core, which is not the case with 14 or 15 . The scarcity of material precluded us from performing the C-10-C-11 closure prior to hydrogenation.