Michael–Michael Ring-Closure Reactions for a Dihapto-Coordinated Naphthalene Complex of Molybdenum

The complex MoTp­(NO)­(DMAP)­(η2-naphthalene) (1; DMAP = 4-(dimethylamino)­pyridine; Tp = tris­(pyrazolyl)­borate) is demonstrated to undergo Michael–Michael ring-closure (MIMIRC) reactions promoted by trimethylsilyltriflate. The resulting hexahydrophenanthrenes are formed stereoselectively, with is...

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Bibliographic Details
Published in:Organometallics 2020-04, Vol.39 (8), p.1404-1412
Main Authors: Myers, Jeffery T, Wilde, Justin H, Sabat, Michal, Dickie, Diane A, Harman, W. Dean
Format: Article
Language:English
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Summary:The complex MoTp­(NO)­(DMAP)­(η2-naphthalene) (1; DMAP = 4-(dimethylamino)­pyridine; Tp = tris­(pyrazolyl)­borate) is demonstrated to undergo Michael–Michael ring-closure (MIMIRC) reactions promoted by trimethylsilyltriflate. The resulting hexahydrophenanthrenes are formed stereoselectively, with isolation of a single dominant isomer. Combining the MIMIRC sequence with an oxidative decomplexation step, the final tricyclics can be synthesized from the naphthalene complex with overall yields between 19 and 50% (for four steps). This reaction sequence is shown to be capable of producing a steroidal core directly from naphthalene, providing access to a biologically relevant carbon framework.
ISSN:0276-7333
1520-6041
DOI:10.1021/acs.organomet.0c00110