Pd(II)-catalyzed formal O–H insertion reaction of diazonaphthoquinones to acetic acid proceeded to afford 1,2-naphthalenediol monoacetates. In the presence of lithium halides, halonaphthols were obtained under the reaction conditions.

Pd(OAc) 2 was found to be an efficient catalyst for the macrocyclization of 1,2-diazonaphthoquinones and cyclic ethers. This transformation serves as an efficient method for the synthesis of protected 1,2-naphthalenediols.

A metal-catalyzed reaction of α-diazocarbonyl compounds with an acid anhydride is reported. In particular, 1,2-naphthalenediol diacetates were synthesized by the reaction of 1,2-

C h emIn fo rm 2 0 1 2 , 4 3 , issu e 1 0 © 2 0 1 2 Wiley -VCH Verl ag G m b H & Co. K G a A , We i n he i m Na pht ho l s Q 0 850 DOI: 1 0.100 2/ch in.201 2100 87 P d ( II) -Catalyzed Formal O-H Ins ertion Rea ctions of D ia zona phthoquinones t o A cetic Acid: Sy nt hesis o f 1 ,2-N a pht ha lenediol D eriv atives. -T he pos ition of the ace tyl g r o up o f the produc ts (I II)/(IV) a nd (VI )/(VII) is un dete rmined alth ough one majo r produc t is obta ined in ge nera l. In the presen ce of lithium halid es halo nap hthols can als o be obta ine d, cf . (X ) . I n this ca se the us e of Pd Cl2 ins tea d of Pd(O Ac )2 give s hi ghe r yi el d s. -( KI T A MUR A*, M. ; KI SA NUK I , M. ; SA KA T A, R. ; OK AUC H I, T . ; C h em. Le tt. 40 ( 2 011) 1 0, 11 29-113 1, http ://dx.do i.org/10 .1246 /cl.2 011.1 129 ; De p. A ppl. C he m ., Fa c. Eng., Kyushu I ns t. T ech nol., T obata , Kitakyu sh u 804 , Ja pan ; Eng.) -C. Gebha rdt 10 -08 7

Conversion of quinone (VI) leads to the desired product (VII) in low yield and imidoyl acetate (VIII) is isolated as the major product.