Biaryl synthesis using highly stablearyl[2-(hydroxymethyl)phenyl]dimethylsilanes and aryl iodides under fluoride-free conditions

Nakao, Yoshiaki; Sahoo, Akhila K.; Yada, Akira; Chen, Jinshui; Hiyama, Tamejiro

doi:10.1016/j.stam.2006.02.019

Cited by 44 publications

(9 citation statements)

References 12 publications

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“…These observations led Hayashi, Hiyama and co-workers to develop mild conditions for the rhodium-catalyzed asymmetric 1,4-arylation and alkenylation [ 155 ]. They employed a series of organo[2-(hydroxymethyl)phenyl]dimethylsilanes [ 156 – 158 ] as organosilicon reagents and they also used these conditions for the 1,4-addition of α,β-unsaturated amides and lactams ( Scheme 17 ).…”

Section: Reviewmentioning

confidence: 99%

Diastereoselective and enantioselective conjugate addition reactions utilizing α,β-unsaturated amides and lactams

Byrd¹

2015

Beilstein J. Org. Chem.

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SummaryThe conjugate addition reaction has been a useful tool in the formation of carbon–carbon bonds. The utility of this reaction has been demonstrated in the synthesis of many natural products, materials, and pharmacological agents. In the last three decades, there has been a significant increase in the development of asymmetric variants of this reaction. Unfortunately, conjugate addition reactions using α,β-unsaturated amides and lactams remain underdeveloped due to their inherently low reactivity. This review highlights the work that has been done on both diastereoselective and enantioselective conjugate addition reactions utilizing α,β-unsaturated amides and lactams.

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Section: Reviewmentioning

confidence: 99%

Diastereoselective and enantioselective conjugate addition reactions utilizing α,β-unsaturated amides and lactams

Byrd¹

2015

Beilstein J. Org. Chem.

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“…Pleasingly, the cross-coupling reactions proceed at room temperature. Although the literature provides many examples of 1-oxa-2-silacyclopentanes reacting to yield products of protodesilylation, [19] oxidative desilylation [9,10] and cross-coupling, [11] few reports of C-alkylation have been described. [15] The saturated oxasilane congener 12 also furnished alkylation products analogous to the type II ARC counterpart with electrophiles 19 a, b, and e; however in these examples, as with the corresponding type II ARC reaction, CuI was not required.…”

Section: Angewandte Chemiementioning

confidence: 99%

Anion Relay Chemistry: Access to the Type II ARC Reaction Manifold through a Fundamentally Different Reaction Pathway Exploiting 1‐Oxa‐2‐silacyclopentanes and Related Congeners

et al. 2011

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Distinctly different: Two 1‐oxa‐2‐silacyclopentenes and a saturated congener have been synthesized and demonstrated to provide access to type II anion relay chemistry (ARC) through a fundamentally new mechanistic pathway. Similar to previous studies, but contrary to initial hypothesis, Brook rearrangement additives (hexamethylphosphoramide and CuI) are necessary to promote Si migration and anion capture.

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“…The synthetic utility of 1‐oxa‐2‐silacyclopentanes and related congeners has been widely recognized by other laboratories. Ito9 and Woerpel10 exploited the Tamao–Fleming oxidation to furnish 1,3‐diols; Hiyama,11a Tamao,11b and Denmark11c,d achieved Hiyama‐type palladium‐catalyzed cross‐coupling reactions induced by fluoride; and both Roush12 and Schreiber13 employed 1‐oxa‐2‐silacyclopentanes as templates for intramolecular Diels–Alder reactions. More recently, Trost14 and Lee15 exploited 1‐oxa‐2‐silacyclopentanes respectively both to access aldol‐type products and to achieve anionic desilylation followed by C‐alkylation, the latter induced by fluoride ion.…”

Section: Methodsmentioning

confidence: 99%

Anion Relay Chemistry: Access to the Type II ARC Reaction Manifold through a Fundamentally Different Reaction Pathway Exploiting 1‐Oxa‐2‐silacyclopentanes and Related Congeners

et al. 2011

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Type I and II anion relay chemistry (ARC) [1] exploiting [1,n]-Brook rearrangements [2] (Scheme 1A and B, respectively), comprise an effective set of synthetic tactics that unite multiple components, in a single reaction flask, that permits rapid access to architecturally diverse polyketide and alkaloid molecular arrays. [2] To extend the ARC concept, we recently designed, synthesized and evaluated a number of new bifunctional linchpins for the type II process, [3] and then demonstrated their utility both in natural product [4] and diversity oriented synthesis (DOS). [5] During the development of the type II multicomponent process, we became intrigued with the possibility of accessing the type II ARC reaction manifold through a fundamentally different pathway employing 1-oxa-2-silacyclopentanes and related congeners (cf. 2, Scheme 2).Based on the structural resemblance of 1-oxa-2-silacyclopentene 2 to the proposed ARC silicon ate intermediate 4, we envisioned that addition of a nucleophile (MeLi) might provide access to the type II reaction products. We were of course cognizant of the elegant observation of Mosher and Brook, [6] that in the [1,2]-Brook rearrangement, charge transfer from the initially derived oxyanion to carbon proceeds through a silicon ate intermediate. [7] However to achieve success with the type II ARC protocol, we learned early on that a change in temperature, solvent polarity, and/or metal ion additive was required to trigger the [1,4]-Brook rearrangement after initial addition of a nucleophile. The presumed silicon ate intermediate [7] then furnishes the reactive anion 5, capable of alkylation, [3d] or in the presence of a palladium catalyst, cross-coupling. [3d,f, 8] By arriving at the silicon ate intermediate through a different pathway (cf. 2→4), we anticipated that the use of such "triggers" might not be required to arrive at 5. That is, access to the pentacoordinate silicon ate species 4, followed by conversion and capture of the resultant anion 5 might only require addition of methyllithium in a compatible solvent (Scheme 2).The synthetic utility of 1-oxa-2-silacyclopentanes and related congeners has been widely recognized by other laboratories. Ito [9] and Woerpel [10] exploited the Tamao-Fleming ** Financial support was provided by the NIH through Grant GM-29028. We thank Drs P. J. Carroll and R. Kohli at the University of Pennsylvania for assistance in obtaining X-ray diffraction and high resolution mass spectra, respectively.

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Biaryl synthesis using highly stablearyl[2-(hydroxymethyl)phenyl]dimethylsilanes and aryl iodides under fluoride-free conditions

Cited by 44 publications

References 12 publications

Diastereoselective and enantioselective conjugate addition reactions utilizing α,β-unsaturated amides and lactams

Diastereoselective and enantioselective conjugate addition reactions utilizing α,β-unsaturated amides and lactams

Anion Relay Chemistry: Access to the Type II ARC Reaction Manifold through a Fundamentally Different Reaction Pathway Exploiting 1‐Oxa‐2‐silacyclopentanes and Related Congeners

Anion Relay Chemistry: Access to the Type II ARC Reaction Manifold through a Fundamentally Different Reaction Pathway Exploiting 1‐Oxa‐2‐silacyclopentanes and Related Congeners

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