Recent advances in stereoselective synthesis involving
diazocarbonyl intermediates

Doyle, Michael P.; McKervey, M. Anthony

doi:10.1039/a604927c

Cited by 75 publications

(31 citation statements)

References 42 publications

(65 reference statements)

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“…Tremendous advances have recently been documented in enantioselective organocatalytic approaches to cyclopropane synthesis,5,19-23 many of which proceed via Michael addition-initiated ring-closure sequences 5,19,24-26. Likewise, impressive progress has been made in the area of metal-catalyzed cyclopropanation of olefins with diazoesters and related precursors to afford enantio- and diastereoenriched cyclopropanes 5,27-29. The third pillar in cyclopropane synthesis is halomethylmetal-mediated cyclopropanation reactions (the Simmons–Smith reaction) 12,17,30-32.…”

Section: Introductionmentioning

confidence: 99%

One-Pot Catalytic Enantio- and Diastereoselective Syntheses ofanti-,syn-cis-Disubstituted, andsyn-Vinyl Cyclopropyl Alcohols

et al. 2009

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Highly enantio-and diastereoselective methods for the synthesis of a variety of cyclopropyl alcohols are reported. These methods represent the first one-pot approaches to syn-vinyl cyclopropyl alcohols, syn-cis-disubstituted cyclopropyl alcohols, and anti-cyclopropyl alcohols from achiral precursors. The methods begin with enantioselective C-C bond formations promoted by a MIB-based zinc catalyst to generate allylic alkoxide intermediates. The intermediates are then subjected to in situ alkoxide-directed cyclopropanation to provide cyclopropyl alcohols. In the synthesis of vinyl cyclopropyl alcohols, hydroboration of enynes is followed by transmetalation of the resulting dienylborane to zinc to provide dienylzinc reagents. Enantioselective addition to aldehydes generates the requisite dienyl zinc alkoxides, which are then subjected to in situ cyclopropanation to furnish vinyl cyclopropyl alcohols. Cyclopropanation occurs at the double bond allylic to the alkoxide. Using this method, syn-vinylcyclopropyl alcohols are obtained in 65-85% yield, 76-93% ee, and >19:1 dr. To prepare anti-cyclopropanols, enantioselective addition of alkylzinc reagents to conjugated enals provides allylic zinc alkoxides. Because direct cyclopropanation provides syn-cyclopropyl alcohols, the intermediate allylic alkoxides were treated with TMSCl/Et 3 N to generate intermediate silyl ethers. In situ cyclopropanation of the allylic silyl ether resulted in cyclopropanation to form the anti-cyclopropyl silyl ether. Workup with TBAF affords the anti-cyclopropyl alcohols in one-pot in 60-82% yield, 89-99% ee, and ≥10:1 dr. For the synthesis of cis-disubstituted cyclopropyl alcohols, in situ generated (Z)-vinyl zinc reagents were employed in asymmetric addition to aldehydes to generate (Z)-allylic zinc alkoxides. In situ cyclopropanation provides syn-cis-disubstituted cyclopropyl alcohols in 42-70% yield, 88-97% ee, and >19:1 dr. These one-pot procedures enable the synthesis of a diverse array of cyclopropyl alcohol building blocks with high enantio-and diastereoselectivities.

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Section: Introductionmentioning

confidence: 99%

One-Pot Catalytic Enantio- and Diastereoselective Syntheses ofanti-,syn-cis-Disubstituted, andsyn-Vinyl Cyclopropyl Alcohols

et al. 2009

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“…For example, diazo groups (R 1 R 2 C=N 2 ) are smaller than analogous azido groups (R 1 R 2 HC–N 3 ), and diazo groups display a broader range of reactivity. 1,2 …”

mentioning

confidence: 99%

Diazo Compounds: Versatile Tools for Chemical Biology

2016

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Diazo groups have broad and tunable reactivity. That and other attributes endow diazo compounds with the potential to be valuable reagents for chemical biologists. The presence of diazo groups in natural products underscores their metabolic stability and anticipates their utility in a biological context. The chemoselectivity of diazo groups, even in the presence of azido groups, presents many opportunities. Already, diazo compounds have served as chemical probes and elicited novel modifications of proteins and nucleic acids. Here, we review advances that have facilitated the chemical synthesis of diazo compounds, and we highlight applications of diazo compounds in the detection and modification of biomolecules.

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“…1,2 Catalytic asymmetric cyclopropanation of diazoacetate with alkene has been one of the most efficient synthetic methods for this kind of compound. Among the efficient catalysts which have been developed, copper-Schiff base complexes derived from chiral amino alcohols are of particular significance because they are effective for the intermolecular cyclopropanation of various substituted olefins including mono-, di-, and trisubstituted olefins, as well as for intramolecular cyclopropanation.…”

Section: Introductionmentioning

confidence: 99%

Asymmetric Cyclopropanation of Styrene Catalyzed by Cu–(Chiral Schiff-Base) Complexes

Liu

Zheng

et al. 2000

Tetrahedron

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Recent advances in stereoselective synthesis involving diazocarbonyl intermediates

Cited by 75 publications

References 42 publications

One-Pot Catalytic Enantio- and Diastereoselective Syntheses ofanti-,syn-cis-Disubstituted, andsyn-Vinyl Cyclopropyl Alcohols

One-Pot Catalytic Enantio- and Diastereoselective Syntheses ofanti-,syn-cis-Disubstituted, andsyn-Vinyl Cyclopropyl Alcohols

Diazo Compounds: Versatile Tools for Chemical Biology

Asymmetric Cyclopropanation of Styrene Catalyzed by Cu–(Chiral Schiff-Base) Complexes

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