Reactions of Group 6 Fischer carbene complexes with alkynes: effect of the metal on the product distribution and the isolation of a nontautomerized cyclohexadienone complex

Wulff, William D.; Bax, Brian M.; Brandvold, Timothy A.; Chan, Kin Shing; Gilbert, Adam M.; Hsung, Richard P.; Mitchell, J. Dale.; Clardy, Jon

doi:10.1021/om00013a021

Cited by 114 publications

(75 citation statements)

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“…Several competent collecting and reviewing articles with many leading references have appeared. 474,478,[849][850][851] Scheme 77 shows some of the more important intermediates along the reaction coordinate toward the product 535. The reaction is very complex, and depending on the reaction conditions and the substituents in the starting components, the product mixture may, besides hydroquinone derived complexes, e.g.…”

Section: [3+2+1]mentioning

confidence: 99%

Metal-Assisted Cycloaddition Reactions in Organotransition Metal Chemistry

1997

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Section: [3+2+1]mentioning

confidence: 99%

Metal-Assisted Cycloaddition Reactions in Organotransition Metal Chemistry

1997

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“…The reaction crude was dissolved in dry hexane, filtered through a pad of Celite and, when the complexes are solids, cooled to À 208 C overnight to induce crystallization. (573,8), (545,10), (517, 57), (300, 100).…”

Section: (Cc)mentioning

confidence: 99%

“…(2R*,4S*,9S*,10R*) 4, (1S*,8R*,11S*,18S*) 18 .0 2,10 .0 3,8 . (1S*,8R*,11S*,13R*,18S*) (1S*,8R*,11S*,13S*,14R*,18S*) 18 .0 2,10 .0 3,8 .0 12,17 ]docosa-2,9,12 17 -triene-15-one (36 g): Diene 1 e (1 mmol) was added to a solution of carbene complex 4 m (2 mmol) in THF (20 mL).…”

Section: -Morpholinomentioning

confidence: 99%

“…(1S*,8R*,11S*,13R*,18S*) (1S*,8R*,11S*,13S*,14R*,18S*) 18 .0 2,10 .0 3,8 .0 12,17 ]docosa-2,9,12 17 -triene-15-one (36 g): Diene 1 e (1 mmol) was added to a solution of carbene complex 4 m (2 mmol) in THF (20 mL). The reaction was allowed to proceed for 4 d, and then concentrated to dryness.…”

Section: -Morpholinomentioning

confidence: 99%

“…(3), Scheme 1]. [10] Moreover, in the reaction of arylamino carbene complexes with alkynes, indene derivatives were reported to be the main products. [11] Since then, Aumann et al have shown several examples of cyclopentadiene formation from metallatrienes, which can be formed by treatment of alkynyl carbene complexes with enamines.…”

Section: Introductionmentioning

confidence: 99%

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Reactions of 2‐Amino‐1,3‐butadienes and Fischer Alkynyl Carbenes: Up to Nine C−C Bonds and Seven Stereogenic Centers Created in a Stereoselective Manner through a Cascade Process

Barluenga

Aznar

Barluenga

et al. 1998

Chemistry A European J

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The reactions of 2-amino-1,3-butadienes 1, 2, and 3 with various substituted Fischer alkynyl carbene complexes are reported. Reaction of 2-aminodienes with alkyl-or silyl-substituted complexes 4 affords cyclohexadienylcarbene complexes 5 or arylcarbene complexes 13. However, when an aryl group is present in the carbene complex instead of the alkyl substituent, the initial [42] cycloaddition is followed by a cyclopentannulation to yield fluorene derivatives 15. The reaction is highly stereoselective and occurs under mild conditions. Substitution of the starting alkynyl carbene complex with a vinyl group produces a similar tandem cycloaddition ± cyclopentannulation. However, in this case, a cyclopentadiene moiety is generated and, hence, a new cycloaddition ± cyclopentannulation sequence can be initiated with another molecule of the starting alkynyl complex. In this way, polycycles 35 and 42 have been synthesized by cascade double and triple [42] cycloaddition ± cyclopentannulation processes by incorporation of two or three equivalents of the carbene complex, respectively.

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