Trimethylsilyl methanenitronate

In the total synthesis of dysidiolide, the a. unsaturated ketone (11) was treated with TMSLi to give exclusively the axial 8-TMS ketone (12) in 64% yield (eq 17). The introduction of the trimethylsilyl group initiates a Brook rearrangement later on in the synthesis, which established the fully substituted bicyclic core of dysidiolide.  

Related Reagents. Dimethyl(phenyl)silane Dimethylphenyl-silyllithium Hexamethyldisilane Trimethylsilyl cuprate Trimethylsilylpotassium. 

Sakurai, H. Okada, A. Kira, M. Yonezawa, K., Tetrahedron Lett. 1971, 1511. 

InChl = lS/C4HllN02Si/cl-5(6)7-8(2,3)4/hlH2,2-4H3 InChIKey = VNEHTFSOCPDKQH-UHFFFAOYSA-N (R = C5H11, R2 = H, RsSi = TBDMS) 

Physical Data R = C5H11, R = H, RsSi = TBDMS bp 80-90 °C/0.02 mmHg. R r2 = (CH2)s, RsSi = TBDMS bp 150 °C/0.01 mmHg. A more complete list of silyl nitronates is given by TorsseU.  

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The formation of trimethylsilyl methanenitronate in the reaction of nitro-methane with trimethylchlorosilane in the presence of pyridine was also postulated without any experimental evidence (173). 

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