A Highly Diastereoselective Synthesis of (1<i>R</i>)-(+)-Camphor-Based Chiral Allenes and Their Asymmetric Hydroboration−Oxidation Reactions

Hung, Shang‐Cheng; Wen, Yen-Fang; Chang, Jia‐Wen; Liao, Chun‐Chen; Uang, Biing‐Jiun

doi:10.1021/jo016201i

Cited by 25 publications

(5 citation statements)

References 34 publications

(10 reference statements)

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“…The two diastereomers were present in a 98/2 ratio, and the mixture was used as such in the next step. Spectral properties were in accordance with literature data …”

Section: Methodssupporting

confidence: 83%

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Three-Step Synthesis of Chiral Spirocyclic Oxaphospholenes

et al. 2017

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Chiral spirocylic oxaphospholenes were prepared in a three-step sequence from chiral pool terpenoid ketones. After addition of a metal acetylide, the resulting propargyl alcohols were converted stereoselectively into their allenylphosphonate counterparts. In the last step, they were conveniently cyclized into spirooxaphospholenes with one equivalent of iodine without purification. When starting from sterically hindered terpenes, allenylphosphonates were also easily obtained but showed to be unreactive or rearranged under these cyclization conditions.

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“…The two diastereomers were present in a 98/2 ratio, and the mixture was used as such in the next step. Spectral properties were in accordance with literature data …”

Section: Methodssupporting

confidence: 83%

“…Spectral properties were in accordance with literature data. 43 (1R,2S,4R)- Synthesis of Chiral Allenylphosphonates 10a−h. Representative Example 10b.…”

Section: ■ Experimental Sectionmentioning

confidence: 99%

Three-Step Synthesis of Chiral Spirocyclic Oxaphospholenes

et al. 2017

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“…Treatment of propargyl carbonate 16 (R 1 = CO 2 Me) to Tsuji’s Pd(0)-catalyzed hydrogenolysis conditions gave allene−yne 15c in 82% yield. Reaction of the propargyl alcohol 16 (R 1 = H) to AlH 3 (generated in situ from LiAlH 4 and AlCl 3 ) gave 15c in 68% yield. While the Tsuji protocol was highest yielding, the direct conversion of the propargylic alcohol using AlH 3 was more convenient for accessing 15c , due the ease of substrate preparation and the relative simplicity of the reaction and subsequent purification.…”

Section: Resultsmentioning

confidence: 99%

A General Synthetic Route to Differentially Functionalized Angularly and Linearly Fused [6−7−5] Ring Systems: A Rh(I)-Catalyzed Cyclocarbonylation Reaction

2008

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Investigations of a Rh(I)-catalyzed cyclocarbonylation reaction reveal its general synthetic utility for accessing highly functionalized tricyclic [6-7-5] linear and angular ring systems from allene-ynes. Three types of allene-ynes were prepared and subjected to Rh(I)-catalyzed cyclocarbonylation conditions. For three series of allene-ynes, the [6-7-5] ring systems were afforded in varying yields depending on the substrate structure. One series of allene-ynes afforded the [6-6-5] ring system possessing an alpha-alkylidene cyclopentenone as a result of a selective reaction with the proximal double bond of the allene.

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“…When steric approach control of the nucleophile is considered, one must consider the stereodirecting effect of the camphyl group, which has been exploited in a number of diastereoselective reactions . The camphyl group has been modified to yield better selectivities in these reactions, and a reversal in asymmetric induction is also noted in a few cases .…”

Section: Introductionmentioning

confidence: 99%

Toward an Understanding of 1,5-Asymmetric Induction during Nucleophilic Addition to (Arene)chromium Tricarbonyl Complexes: Conformational Preference of the Chromium Tricarbonyl Tripod for Transmission of Chirality

et al. 2008

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Asymmetric induction during enolate nucleophile addition to chromium tricarbonyl complexes of 4-alkoxy-1-(trimethylsilyl)benzene derivatives, in which the alkoxy group (R*O) is derived from an optically pure alcohol, is analyzed in terms of the effect of the chiral auxiliary (R*) on the conformation of the tricarbonylchromium tripod. Crystal structure determination on the three complexes 3a (R* ) 2-phenylisobornyl), 3b (R* ) 2-methylisobornyl), and 3c (R* ) 2-(3-[1,3]-dioxalanyl)isobornyl) reveals that the chiral group R* causes a rotation of the Cr(CO) 3 group from the normally preferred orientation, the extent and direction of which are dependent on the auxiliary. NMR studies on seven complexes indicate the presence of a single conformation in solution for each, which is assumed to be the same as that shown in the solid state. There is a correlation between the observed asymmetric induction and the Cr(CO) 3 tripod rotation, which is believed to be a result of the effect of this conformational distortion on the arene-centered FMO coefficients.

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A Highly Diastereoselective Synthesis of (1R)-(+)-Camphor-Based Chiral Allenes and Their Asymmetric Hydroboration−Oxidation Reactions

Cited by 25 publications

References 34 publications

Three-Step Synthesis of Chiral Spirocyclic Oxaphospholenes

Three-Step Synthesis of Chiral Spirocyclic Oxaphospholenes

A General Synthetic Route to Differentially Functionalized Angularly and Linearly Fused [6−7−5] Ring Systems: A Rh(I)-Catalyzed Cyclocarbonylation Reaction

Toward an Understanding of 1,5-Asymmetric Induction during Nucleophilic Addition to (Arene)chromium Tricarbonyl Complexes: Conformational Preference of the Chromium Tricarbonyl Tripod for Transmission of Chirality

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