Alkyne Competition in the Benzannulation Reaction with Chromium Carbene Complexes

Abstract

The benzannulation reaction of Fischer carbene complexes is investigated under conditions where the reaction of the carbene complex is occurring in the presence of two different alkynes. A series of competition experiments are examined where the effects of various structural factors are explored by pitting 10 different carbene complexes with 11 different alkynes. Terminal alkynes will react selectively over internal alkynes in all cases examined including both aryl and alkenyl complexes. Aryl carbene complexes with methoxy substituents do not give quite as high selectivity for terminal alkynes over internal alkynes (∼95:5) as do isopropoxy substituents (>99:1), whereas most alkenyl complexes give high selectivity with both substituents (>99:1). Competition experiments between two different terminal alkynes or between two different internal alkynes did not result in anything more than very modest selectivities at best (∼2:1). Excellent selectivities were realized between two different terminal acetylenes if one of the terminal acetylene was protected with a trimethylsilyl group. Finally, it was demonstrated that the high selectivities between terminal and internal alkynes can be utilized in the reaction with molecules that contain both types of alkyne functions.

CuBr-mediated synthesis of 1,4-naphthoquinones via ring expansion of 2-aryl-1,3-indandiones

“…2 With these appealing utilities in mind, many synthetic strategies toward 1,4-NQs have been developed, including the Diels–Alder reaction of substituted 1,3-dienes with preexisting quinones, 3 the reaction of alkynes with metal carbonyls, 4 thermo cycloisomerization of cyclobutenones, 5 and the annulation of Fischer carbene complexes with alkynes. 6 Recently, Li et al reported an efficient transformation of 1,6-enynes into 1,4-naphthoquinones involving a Cu( ii )-catalyzed oxidative carbocyclization. 7 Later, Mal et al described a demethoxycarbonylative annulation of 3-nucleofugal phthalides with α -substituted acrylates to provide a succinct route to 1,4-NQs.…”

Synthesis of 4,4-Dimethyl-1,6-heptadiyne and Alcyopterosin O

“…The monosilylated diyne precursor to 1 provides an opportunity to introduce additional substituents before or after the last step (desilylation) to produce different substitution patterns in the 1,6-diynes. Monosubstitution at the termini of 1,6-heptadiynes is nontrivial, so having this nonsymmetrical intermediate for functional diversification is important. These processes mark the beginning of several target-oriented synthesis efforts, including alcyopterosin E, alcyopterosin A, illudinine, and granulolactone…”