Described herein is the development of an organoaluminium‐mediated tandem conjugate addition‐cyclization sequence of p‐quinone monoacetals with 2‐siloxyphenyl Grignard reagents to afford a collection of phenol‐bridged cyclohexanone derivatives. Furthermore, a tandem conjugate‐addition and dimerization reaction of p‐quinone monoacetals with Grignard reagents is also reported to offer a straightforward and diastereoselective synthesis of complex bridged‐ring compounds bearing tricyclo[6.2.2.02,7]dodecene skeletons.
The copper‐catalyzed reaction of α‐halo‐N‐tosylhydrazones with H‐phosphoryl compounds is reported to afford alkenylphosphoryl compounds in modest to good yields. The reaction may take place via a copper‐promoted Bamford‐Stevens‐type reaction of an α‐phosphorylated diazo intermediate. The diazo intermediate is trapped by an excess H‐phosphoryl compound to give α, N‐bisphosphoryl hydrazone in the absence of a copper catalyst.
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