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Article

Catalytic Amphiphilic Allylation via Bis-π-allylpalladium Complexes and Its Application to the Synthesis of Medium-Sized Carbocycles

Supporting Info

Hiroyuki Nakamura, Kouichi Aoyagi, Jae-Goo Shim, and Yoshinori Yamamoto*

Contribution from the Department of Chemistry, Graduate School of Science, Tohoku University, Sendai 980-8578, Japan

J. Am. Chem. Soc., 2001, 123 (3), pp 372–377

DOI: 10.1021/ja002931g

Publication Date (Web): December 22, 2000

In papers with more than one author, the asterisk indicates the name of the author to whom inquiries about the paper should be addressed.

Abstract

The reaction of certain activated alkenes 3 with allyltributylstannane (4) and allyl chloride (5a) in the presence of palladium catalyst gave the bis-allylation products, 1,7-octadiene derivatives 6a−k, in good to high yields. The reaction of certain imines 9 with 4 and 5a under similar conditions as above afforded the bis-allylated amines, N-allyl-N-3-butene-1-amine derivatives 10a−f, in good to high yields. The bis-allylation reactions most probably proceed through bis-π-allylpalladium intermediate 2. The above intermolecular bis-allylation was extended to the intramolecular reaction. The reaction of 8-chloro-2,6-octadienyltributylstannane (17a) with activated alkenes 3 gave a mixture of regioisomeric cycloadducts, [8+2] and [4+2] cycloaddition products. The regioisomeric ratio was dependent on solvent and the electron density at the β-position of activated alkenes. In general, the [8+2] cycloadducts 18 were obtained predominantly in CH₂Cl₂, whereas the [4+2] adducts 24 and 25 were produced predominantly in DMF. The reaction of 7-chloro-2,8-nonadienyltributylstannane (17b) with activated alkenes gave selectively the [9+2] cycloadducts 19 and 22: the regioisomeric [5+2] and [7+2] adducts were not obtained at all. The reaction of 10-chloro-2,8-decadienyltributylstannane (17c) with activated alkene 3a afforded the [10+2] cycloadducts 20 and 23 in low yields. The mechanism on the intramolecular bis-allylation reaction is discussed.