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Cyclobut‐2‐enones from Alkynes via Dichlorocyclobut‐2‐enones
Author(s) -
Ammann Adrian A.,
Rey Max,
Dreiding André S.
Publication year - 1987
Publication title -
helvetica chimica acta
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.74
H-Index - 82
eISSN - 1522-2675
pISSN - 0018-019X
DOI - 10.1002/hlca.19870700208
Subject(s) - chemistry , isomerization , pyridine , medicinal chemistry , enone , double bond , cycloaddition , stereochemistry , organic chemistry , catalysis
The [2 + 2]‐cycloaddition of dichloroketene (prepared in situ from CCl 3 COCl and Zn(Cu)) with three alkynes 1a–c to form 2,3‐dimethyl‐( 2a ), 2,3‐diethyl‐( 2b ) and 3‐butyl‐4,4‐dichlorocyclobut‐2‐enone ( 2c ) proceeds rapidly in the absence of POCl 3 . The primary products 2a–c rearrange in situ to the 2,4‐dichlorocyclobut‐2‐enones 3a–c under the influence of ZnCL 2 produced during the reaction. ZnCl 2 converts both 2a and 3a into a 4:6 equilibrium mixture of the two; this isomerization does not occur with LiCl. The Cl‐atoms of both 2a , b and 3a , b and of 2c may reductively be removed with Zn(Cu) in AcOH/pyridine to afford the alkylcyclobutenones 4a‐c . Without pyridine, this reduction gives ca. 1:1 mixtures of the double‐bond isomers 4 and 5 in low yields. The cyclobutenones 2c and 4c may be deuterated by CD 3 COOD in the presence of pyridine. D ‐Atom is introduced into 2c at C(4) and at C(γ), and into 4c at C(2) and C(4). A mechanism for this deuteration is considered, which does not involve a cyclobutadienolate 7 , but rather a cyclobutenolate of type 8 . The reductions of 2 and 3 to 4 might also pass through the same type of intermediate 8 .