Tandem cyclization-cycloaddition reactions of .alpha.-diazoacetophenone derivatives

Padwa, Albert; Carter, Stephen P.; Nimmesgern, Hildegard

doi:10.1021/jo00357a050

Cited by 73 publications

(15 citation statements)

References 4 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Carbonyl ylide formation followed by intramolecular cycloaddition resulted in tricyclic product 56a, Eq. 39 [66][67][68][69]. Cycloaddition also occurred with the amide analogue 55 b.…”

Section: Cycloadditions Of Cyclic Carbonyl Ylidesmentioning

confidence: 99%

Using ring-opening reactions of oxabicyclic compounds as a strategy in organic synthesis

Chiu

Lautens

1997

Topics in Current Chemistry

149

View full text Add to dashboard Cite

“…Carbonyl ylide formation followed by intramolecular cycloaddition resulted in tricyclic product 56a, Eq. 39 [66][67][68][69]. Cycloaddition also occurred with the amide analogue 55 b.…”

Section: Cycloadditions Of Cyclic Carbonyl Ylidesmentioning

confidence: 99%

Using ring-opening reactions of oxabicyclic compounds as a strategy in organic synthesis

Chiu

Lautens

1997

Topics in Current Chemistry

149

View full text Add to dashboard Cite

“…In 1986 we started work in our laboratory 5 to synthesize bridged hetero-substituted bicycloalkanes from the rhodium(II)-catalyzed cyclization/cycloaddition cascade of 1-diazoalkanediones. 6 The cascade process was shown to proceed by the formation of a rhodium carbenoid intermediate.…”

Section: Carbonyl Ylide Cycloadditionsmentioning

confidence: 99%

“…Subsequent transannular cyclization of the electrophilic carbenoid onto the adjacent keto group generates a cyclic carbonyl ylide dipole and this is followed by a 1,3-dipolar cycloaddition reaction. 5 The primary spatial requirement for carbonyl ylide formation is that the distance between the two reacting centers be sufficiently close so that effective overlap of the lone pair of electrons on the carbonyl group with the metallocarbenoid can occur. Most of our earlier studies were carried out with five-and six-membered ring systems.…”

Section: Carbonyl Ylide Cycloadditionsmentioning

confidence: 99%

Domino reactions of rhodium(ii) carbenoids for alkaloid synthesis

Padwa¹

2009

Chem. Soc. Rev.

Self Cite

399

104

View full text Add to dashboard Cite

In this tutorial review, the rhodium(II)-catalyzed domino reactions of alpha-diazo carbonyl compounds are summarized. The article will emphasize some of the more recent synthetic applications of the rhodium carbenoid cyclization/cycloaddition domino cascade for alkaloid synthesis. The many structurally diverse and highly successful examples of both oxa and azapolycyclic ring formation cited in this tutorial review clearly demonstrate that the domino cyclization/cycloaddition cascade of metallo carbenoids has evolved as an important strategy for the synthesis of nitrogen containing natural products.

show abstract

“…12,13 It has found particularly frequent use for the in situ generation of carbonyl ylides. 14,15 Thus, the first step in the synthesis of 1,3-oxaphospholes described here is most probably the formation of the reactive rhodium carbenoid 11 from the diazo compound 7 under the action of rhodium(II) acetate.…”

mentioning

confidence: 99%

Organophosphorus Compounds, Part 149. Preparation of 1,3-Oxaphospholes by Transition Metal-Catalyzed Reactions of α-Diazo-β-dicarbonyl Compounds with tert-Butylphosphaacetylene

Ruf¹,

Mack²,

Steinbach³

et al. 2000

Synthesis

View full text Add to dashboard Cite

In the presence of Rh 2 (OAc) 4 as catalyst the cyclic a-diazo-b-dicarbonyl compounds 7a-c react with tert-butylphosphaacetylene 2 under elimination of nitrogen to furnish the 1,3-oxaphosphole derivatives 8a-c. The feasible competing reaction with formation of the 1,2,4-diazaphospholes 9a-c has not been observed.The class of the 1,3-oxaphospholes still constitutes a relatively unknown area in the fertile field of heterophosphole chemistry. 2 Currently, only two separate routes to nonbenzo-condensed 1,3-oxaphospholes have been described: Thus, 1,3-oxaphosphole derivatives can be obtained either by reaction of phosphaacetylenes with Fischer-type chromium carbene complexes or by 1,3-dipolar cycloaddition reactions of isomünchnones with the phosphaacetylenes. [3][4][5] Although the reaction of the isomünchnone 5 with the phosphaacetylene 2 furnishes the 1,3-oxophosphole derivative 6 in very good yield in a highly specific reaction, 3,4 the 1,3-oxaphosphole 3 prepared from the carbene complex 1 is isolated in merely 35% yield. 5 The reason for this low yield is the fact that the reaction is not specific for formation of the 1,3-oxaphosphole but is instead accompanied by a side reaction furnishing the phosphaarene species 4. 5 By use of catalytic amounts of rhodium(II) acetate we have now successfully realized reactions between the cyclic a-diazo-b-dicarbonyl compounds 7 and tert-bu- Scheme 1Downloaded by: National University of Singapore. Copyrighted material.

show abstract

Tandem cyclization-cycloaddition reactions of .alpha.-diazoacetophenone derivatives

Cited by 73 publications

References 4 publications

Using ring-opening reactions of oxabicyclic compounds as a strategy in organic synthesis

Using ring-opening reactions of oxabicyclic compounds as a strategy in organic synthesis

Domino reactions of rhodium(ii) carbenoids for alkaloid synthesis

Organophosphorus Compounds, Part 149. Preparation of 1,3-Oxaphospholes by Transition Metal-Catalyzed Reactions of α-Diazo-β-dicarbonyl Compounds with tert-Butylphosphaacetylene

Contact Info

Product

Resources

About