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The diastereoselectivity of the formation of 4 could be
rationalized using 4a as the substrate through theoretical
calculations. Based upon DFT calculations (B3LYP/6-311),
the Dreiding models showed that the intermediate 7a adopts a
conformation with the lowest energy in which the Me group
on C5 is located in the plane of CQO, C4–C5 and C5–Me, and
syn to the phenyl group on C1 (Scheme 6). Sequential ring
closure through the C–C bond formation between C1 and C5
led to the final product 4a with syn-phenyl, Me groups.
Benzocyclobutanone and indanone derivatives are versatile
synthetic intermediates in total synthesis of natural products
with a variety of types of carbon skeletons.13 Therefore, to
demonstrate the synthetic potential of the photochemical
formation of these compounds, a solution of 500 mg of
aromatic g,d-epoxy ketone 1a and 3a in 150 mL of anhydrous
benzene was irradiated to 100% conversion to afford 2a and
4a in 67% and 59% yield respectively.
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In conclusion, the photochemistry of terminal and substituted
aromatic g,d-epoxy ketones in benzene solution was investigated.
The work reported in this communication provides an easy access
to benzocyclobutanones and indanones, and highlights the
application of photochemistry in the realm of organic synthesis.
We are continuing to explore the scope of this transformation
as well as further mechanistic investigations.
We are grateful for the financial support from China NSFC
(Nos 21002018 and 21072038), the Fundamental Research
Funds for the Central Universities (No. HIT.BRET2.2010001),
WZSTP (No. G20100056) and ZJSTP (No. 2011C23116).
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