Dihydrobenzopyran and dihydrobenzofuran ring systems, are important motifs in biologically active

natural products and pharmaceutical drug targets. In order to yield cost efficient dihydrobenzopyran and
dihydrobenzofuran ring systems, mild, efficient, and economical Ag(I)-catalyzed sequential C-C/C-O bond
formations between phenols and dienes were developed.

a transition-metal-catalyzed reaction can directly construct complicated molecules from readily

accessible starting materials under mild conditions. Earlier silver(I) complex was believed to have low
catalytic efficiency and were used as cocatalysts or Lewis acids. But recently Ag(I) catalysed reaction are
emerging.The intramolecular hydroalkoxylation is an attractive approach to the synthesis of cyclic
ethers.Therefore, the addition of the OH groups of phenols across dienes to get dihydrobenzopyran or
dihydrobenzofuran ring systems was predicted. Generally dihydrobenzopyrans are prepared in two steps
from allyl aryl ethers and dihydrobenzofurans are constructed typically from arene-ene substrates or by
cycloaddition of o-quinonemethides. Moreover, previously reported synthetic methods for the 1:1
addition of a phenol across a diene usually give a complicated mixture of several products. It was very
rare to find efficient and clean process for this reactions.Authors were interested in developing a one-pot
synthesis of dihydrobenzopyrans and dihydrobenzofurans from phenols and dienes, whereby a single
catalytic system would invoke sequential C-C and C-O bond formations with high efficiency and complete
atom economy.The discovery of AgOTf for the sequential addition/cyclization of phenols with dienes in
an economic manner, is reported.

Initially the reaction between p-methoxyphenol and isoprene were selected as the first substrates for
screening of several metal salts and complexes. Transition metal complexes which earlier were known to
promote hydroarylation and hydroalkoxylation or activate the alkenes were included in the screen. It was
discovered that 5 mol % of AgOTf was optimal in this reaction system to produce dihydrobenzopyran 1 in
60% yield. After examing various solvent, ClCH2CH2Cl appeared preferable. Other transition metal
complexes which were used for screening either not effective or produced low yield. In the presence of
phosphine ligand the reaction occurred but there was no increase in yield of 1. In addition, a catalytic
amount of TfOH (5 mol %) did result in the production of 1, but only 18% . These results showed that
silver plays an important role in this coupling process.

to explore the scope of this coupling process, a variety of phenols i.e both electron rich and electron
deficient (As shown in Table 2) underwent tandem addition/cyclization in the presence of AgOTf to form
the corresponding dihydrobenzopyrans. Similarly range of dienes were examined for the reaction.Good
yields were obtained for all cases. With the exception of 2,3-dimethyl-1,3-butadiene, all dienes gave the
corresponding dihydrobenzofurans as the sole products.

Regioselectivity observed in Ag(I) catalyzed reaction is found to be similar to that of Al, Pd, Pt, and Au
catalyzed reaction of alcohols (or amines) with dienes, which suggests that C-C/C-O bond formation
occurs by a similar mechanism in those reactions. Based on similar mechanism shown for Al, Au and Ag
catalyzed reactions of alcohols with C=C bonds, a possible mechanism for Ag(I)-catalyzed sequential
addition/cyclization (Scheme 1) is proposed. Dienes are activated by coordination of Ag(I) is followed by
intermolecular nucleophilic attack by the arene. The resulting Ag-C bond is protonated to give the 2-
allylphenol intermediate. Then recoordination of C-C π-bond by Ag(I) activates the olefin toward
intramolecular nucleophilic attack by the phenolic oxygen. Subsequent proton transfer produces the final
product and regenerates the Ag(I) catalyst.

To conclude a mild and efficient Ag(I)-catalyzed sequential C-C/C-O bond formations between phenols
and dienes is developed to give dihydrobenzopyran and dihydrobenzofuran ring systems. Both electron-
rich and electron-deficient phenols successfully underwent this reaction, and both cyclic and acyclic
dienes could be applied. silver(I) is economic relative to other expensive transition metals employed
previously to promote this reactions. This one-pot reaction helps in construction of dihydrobenzopyran
and dihydrobenzofuran ring systems, which are important motifs in both naturally occurring and
biologically active compounds.

1,4-naphthoquinones and anthracyclinones, which are versatile intermediates in the synthesis of

biologically active compounds are formed by providing convenient access to ortho-allyl phenols and
naphthols, through the [3,3] sigmatropic shift (Claisen rearrangement) of allyl aryl ethers.

The difficulty in preparing 2,2-disubstituted ethers such as 1', suggest that for the preparation of
terminally substituted ortho-allylphenols 2, Claisen rearrangement is not convenient. Therefore as an
alternative to the Claisen rearrangement (Equation 1) A mild and convenient method for the [1,3]
rearrangement of ether 1 was needed.

In spite of the fact that [1,3] rearrangement is an efficient synthetic method for preparation of ortho- or
para-prenylated phenols along with chroman derivatives 3, it usually requires high temperatures to
proceed. Which condition leading to severe side reactions. Bismuth compounds recently reported to be
used as catalyst in many reactions, due to their low toxicity, low cost, and good stability. Bi(OTf)3 is
particularly attractive since it is commercially available or can be easily prepared. Bi(OTf)3 behaves like
Lewis acid, which helped to study desired [1,3] shift. It was found that [1,3] rearrangement of
substituted 3-methylbut-2-enyl naphthyl ethers was efficiently catalyzed by Bi(OTf)3·4H2O in mild
conditions. Both ortho- and paraprenylated naphthols and phenols are readily obtained in the presence
of 5 mol% of Bi(OTf)3 and gave best yield without showing Claisen [3,3] rearrangement

Initially, the [1,3] rearrangement on differently 2- and 4-substituted allyl 1-naphthyl ethers (Table 1)
were screened. The substituted 1-naphthyl prenyl ethers 5a–d, were made to react with mol%
Bi(OTf)3·4H2O in an apolar solvent such as toluene (Scheme 1). The ortho- and para-substituted
naphthol derivatives 6 and 8, along with the corresponding chroman derivatives 7 were isolated in
moderate to good yields. Whatever the substitution of the naphthol ring, the reaction occurred
smoothly to give the corresponding ortho- or para-prenylnaphthols 6 or 8 (Table 1, entries a– c). 1-
Naphthyl prenyl ether 5a gives orthoprenylnaphthol (6a) (Table 1, entry a). [1,3] rearrangement with
ortho-substituted 1-naphthyl prenyl ethers, gives corresponding para-prenylnaphthols 8b (Table 1, entry
b) and 1-(3-Methylbut-2- enyloxy)-4-methoxynaphthalene (5c) gives ortho isomer 6c (Table 1, entry c). 4-
chloronaphthyl prenyl ether immediately followed a cyclization reaction after transfer of the allyl group
in a [1,3] fashion to yield 7d (Table 1, entry d).

The study of scope and limitations of this reaction with differently substituted 3-methylbut-2-enyl
phenyl ethers 1 (Scheme 2) was done. It was made to react with 5 mol% of Bi(OTf)3·4H2O in toluene to
obtain respective para-prenylphenols 4 (Table 2, entries a, b, and g). With para-substituted substrates,
the [1,3] rearrangement immediately followed by a subsequent cationic cyclization occurred in moderate
to good yields to give chroman derivatives 3 (Table 2, entries c–f).

It is found that the reaction condition promotes formation of discrete, delocalized prenyl carbocation
and bismuth aryloxide, which recombine to give the desired product. The detailed mechanism is under
study.

To conclude it was found that Bi(OTf)3·4H2O is an efficient catalyst for the [1,3] rearrangement of aryl
prenyl ethers. It is an economical and is environmental friendly catalyst which uses mild conditions and
doesn't form any hazardous by-products.