Synthesis of the C(7)-C(22)-Sector of (+)-Acutiphycin Via O-Directed Double Free Radical Alkyne Hydrostannation with Ph3SnH/Et3B, Double I-Sn Exchange and Double Stille Coupling

Karl J. Hale, Maciej Maczka, Amarjit Kaur, Soraya Manaviazar, Mehrnoosh Ostovar, Milosz Grabski

Research output: Contribution to journalLetter

9 Citations (Scopus)

Abstract


Abstract Image

Herein a new double O-directed free radical hydrostannation reaction is reported on the structurally complex dialkyldiyne 11. Through our use of a conformation-restraining acetal to help prevent stereocenter-compromising 1,5-H-atom abstraction reactions by vinyl radical intermediates, the two vinylstannanes of 10 were concurrently constructed with high stereocontrol using Ph3SnH/Et3B/O2. Distannane 10 was thereafter elaborated into the bis-vinyl iodide 9 via O-silylation and double I–Sn exchange; double Stille coupling of 9, O-desilylation, and oxidation thereafter furnished 8.
Original languageEnglish
Pages (from-to) 1168-1171
Number of pages4
JournalOrganic Letters
Volume16
Issue number4
Early online date06 Feb 2014
DOIs
Publication statusPublished - 2014

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Free radical reactions
Acetals
Alkynes
alkynes
free radicals
Free Radicals
Conformations
sectors
vinyl radical
acetals
Atoms
Oxidation
synthesis
iodides
oxidation
atoms
acutiphycin
vinyl iodide

Cite this

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title = "Synthesis of the C(7)-C(22)-Sector of (+)-Acutiphycin Via O-Directed Double Free Radical Alkyne Hydrostannation with Ph3SnH/Et3B, Double I-Sn Exchange and Double Stille Coupling",
abstract = "Abstract ImageHerein a new double O-directed free radical hydrostannation reaction is reported on the structurally complex dialkyldiyne 11. Through our use of a conformation-restraining acetal to help prevent stereocenter-compromising 1,5-H-atom abstraction reactions by vinyl radical intermediates, the two vinylstannanes of 10 were concurrently constructed with high stereocontrol using Ph3SnH/Et3B/O2. Distannane 10 was thereafter elaborated into the bis-vinyl iodide 9 via O-silylation and double I–Sn exchange; double Stille coupling of 9, O-desilylation, and oxidation thereafter furnished 8.",
author = "Hale, {Karl J.} and Maciej Maczka and Amarjit Kaur and Soraya Manaviazar and Mehrnoosh Ostovar and Milosz Grabski",
year = "2014",
doi = "10.1021/ol500050p",
language = "English",
volume = "16",
pages = "1168--1171",
journal = "Organic Letters",
issn = "1523-7060",
publisher = "American Chemical Society",
number = "4",

}

Synthesis of the C(7)-C(22)-Sector of (+)-Acutiphycin Via O-Directed Double Free Radical Alkyne Hydrostannation with Ph3SnH/Et3B, Double I-Sn Exchange and Double Stille Coupling. / Hale, Karl J.; Maczka, Maciej; Kaur, Amarjit; Manaviazar, Soraya; Ostovar, Mehrnoosh ; Grabski, Milosz.

In: Organic Letters, Vol. 16, No. 4, 2014, p. 1168-1171.

Research output: Contribution to journalLetter

TY - JOUR

T1 - Synthesis of the C(7)-C(22)-Sector of (+)-Acutiphycin Via O-Directed Double Free Radical Alkyne Hydrostannation with Ph3SnH/Et3B, Double I-Sn Exchange and Double Stille Coupling

AU - Hale, Karl J.

AU - Maczka, Maciej

AU - Kaur, Amarjit

AU - Manaviazar, Soraya

AU - Ostovar, Mehrnoosh

AU - Grabski, Milosz

PY - 2014

Y1 - 2014

N2 - Abstract ImageHerein a new double O-directed free radical hydrostannation reaction is reported on the structurally complex dialkyldiyne 11. Through our use of a conformation-restraining acetal to help prevent stereocenter-compromising 1,5-H-atom abstraction reactions by vinyl radical intermediates, the two vinylstannanes of 10 were concurrently constructed with high stereocontrol using Ph3SnH/Et3B/O2. Distannane 10 was thereafter elaborated into the bis-vinyl iodide 9 via O-silylation and double I–Sn exchange; double Stille coupling of 9, O-desilylation, and oxidation thereafter furnished 8.

AB - Abstract ImageHerein a new double O-directed free radical hydrostannation reaction is reported on the structurally complex dialkyldiyne 11. Through our use of a conformation-restraining acetal to help prevent stereocenter-compromising 1,5-H-atom abstraction reactions by vinyl radical intermediates, the two vinylstannanes of 10 were concurrently constructed with high stereocontrol using Ph3SnH/Et3B/O2. Distannane 10 was thereafter elaborated into the bis-vinyl iodide 9 via O-silylation and double I–Sn exchange; double Stille coupling of 9, O-desilylation, and oxidation thereafter furnished 8.

U2 - 10.1021/ol500050p

DO - 10.1021/ol500050p

M3 - Letter

VL - 16

SP - 1168

EP - 1171

JO - Organic Letters

JF - Organic Letters

SN - 1523-7060

IS - 4

ER -