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19.5.6.3 Method 3: Substitution of a Carbonyl Group by Direct Displacement

DOI: 10.1055/sos-SD-019-00137

Subramanian, L. R.Science of Synthesis, (200419208.

The transformation of ketones 48 into nitriles 49 is an interesting process as a homologated product with one additional carbon is obtained. The technique using 4-toluenesulfonyl isocyanide[‌36‌,‌37‌] demands the use of a strong base such as potassium tert-butoxide (Scheme 18). The mechanism of transformation of an oxo group into a nitrile involves several steps.[‌38‌] The experimental one-step synthesis of nitriles from ketones has been used in the synthesis of natural products, e.g. paniculidine A and B,[‌39‌] ketoprofen,[‌40‌] and cannabinoid derivatives,[‌41‌] to mention a few. The intermediate nitrile 51, involved in the synthesis of paniculidine A, is prepared by this method from ketone 50 in 84% yield (Scheme 18).[‌39‌]

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M e Meeeeeee Meeeeeeeeee (8888) Meeee (%) ee 88 eeee 88 Mee
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MM8 8 ee 88 [‌88‌]
MM8 8 88°M 88 [‌88‌]
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Meee eeeeeee 88 eee eeeeeeeee eee eeeee eeeeeeeeeeeeeeee 88 eeee eeeeeeee 88 ee eeeeeeee eeee eeeeeeeeee eeeeeeeeeee (Meeeee 88);[‌88‌] eeeeeee eeee eeeeeee eee eee eeeeee eeeeeeeee, eeee eeeeee ee eeee eeeeeeeeee eeee eeeeee eeeeeeeee.

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Meeeee 88 Meeeeeeeeee ee 8-Meeeeeeeee[8.8.8]eeeeee-8-eeeeeeeeeeee[‌88‌]

Meeeeeeeeeee Meeeeeeee

Meeeeeee 88; Meeeeee Meeeeeeee:[‌88‌]

MMMMMMM: Meeeeee eeeee eee ee eeeeeeee eeeeeee eee eeee eee eee eeeeeeeee eeeee.

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Meeeeeee 88 eeee Meeeeee 88; Meeeeee Meeeeeeee:[‌88‌]

MMMMMMM: Meeeeee eeeee eee ee eeeeeeee eeeeeee eee eeee eee eee eeeeeeeee eeeee.

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References


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