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. 2016 Oct 26;138(42):13846-13849.
doi: 10.1021/jacs.6b09240. Epub 2016 Oct 13.

Highly Efficient Cascade Reaction for Selective Formation of Spirocyclobutenes from Dienallenes via Palladium-Catalyzed Oxidative Double Carbocyclization-Carbonylation-Alkynylation

Youai Qiu  1 , Bin Yang  1 , Can Zhu  1 , Jan-E Bäckvall  1
Affiliations

Highly Efficient Cascade Reaction for Selective Formation of Spirocyclobutenes from Dienallenes via Palladium-Catalyzed Oxidative Double Carbocyclization-Carbonylation-Alkynylation

Youai Qiu et al. J Am Chem Soc. .

Abstract

A highly selective cascade reaction that allows the direct transformation of dienallenes to spirocyclobutenes (spiro[3.4]octenes) as single diastereoisomers has been developed. The reaction involves formation of overall four C-C bonds and proceeds via a palladium-catalyzed oxidative transformation with insertion of olefin, olefin, and carbon monoxide. Under slightly different reaction conditions, an additional CO insertion takes place to give spiro[4.4]nonenes with formation of overall five C-C bonds.

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Conflict of interest statement

The authors declare no competing financial interest.

Figures

Scheme 1
Scheme 1. Previous Work and Present Work
Scheme 2
Scheme 2. Initial Attempt
Scheme 3
Scheme 3. Scope for Formation of 3,
The reaction was conducted in MeCN at 80 °C using 1 (0.2 mmol), 2a (1.5 equiv), F4-BQ (1.1 equiv) in the presence of Pd(TFA)2 (5 mol %). For stereochemical assignment of products by NOE, see Supporting Information (p. S31).
Scheme 4
Scheme 4. Scope for Formation of 4
The reaction was conducted in DCE at room temperature using 1 (0.2 mmol), 2 (1.5 equiv), and BQ (1.1 equiv) in the presence of Pd(TFA)2 (5 mol %).
Scheme 5
Scheme 5. Kinetic Isotope Effect Studies
Reaction conditions: allene 1a (or 1a-d6) (0.2 mmol), Pd(TFA)2 (5 mol %), F4-BQ (1.1 equiv), and phenylactylene 2a (1.5 equiv) in CD3CN under CO (1 atm) at 80 °C.
Scheme 6
Scheme 6. Proposed Mechanisms
See this image and copyright information in PMC

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