Asymmetric Total Synthesis of (+)-Inthomycin C Via O-Directed Free Radical Alkyne Hydrostannation with Ph3SnH and Catalytic Et3B: Reinstatement of the Zeeck-Taylor (3R)-Structure for (+)-Inthomycin C

Karl J. Hale, Milosz Grabski, Soraya Manaviazar, Maciej Maczka

Research output: Contribution to journalLetter

24 Citations (Scopus)

Abstract

A new pathway to (+)-inthomycin C is reported that exploits an O-directed free radical hydrostannation reaction on (−)-12 and a Stille cross-coupling as key steps. Significantly, the latter process was effected on 19 where a gauche-pentane repulsive interaction could interfere. Our stereochemical studies on the alkynol (−)-12 and the enyne (+)-7 confirm that Ryu and Hatakeyama’s (3S)-stereochemical revision of (+)-inthomycin C is invalid and that Zeeck and Taylor’s original (3R)-stereostructure for (+)-inthomycin C is correct.
Original languageEnglish
Pages (from-to)1164-1167
Number of pages4
JournalOrganic Letters
Volume16
Issue number4
Early online date06 Feb 2014
DOIs
Publication statusPublished - 2014

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Alkynes
pentanes
cross coupling
alkynes
free radicals
Free Radicals
synthesis
Free radical reactions
interactions
inthomycin C

Cite this

@article{58768c5fe3364b44a79a3d58d7b823c2,
title = "Asymmetric Total Synthesis of (+)-Inthomycin C Via O-Directed Free Radical Alkyne Hydrostannation with Ph3SnH and Catalytic Et3B: Reinstatement of the Zeeck-Taylor (3R)-Structure for (+)-Inthomycin C",
abstract = "A new pathway to (+)-inthomycin C is reported that exploits an O-directed free radical hydrostannation reaction on (−)-12 and a Stille cross-coupling as key steps. Significantly, the latter process was effected on 19 where a gauche-pentane repulsive interaction could interfere. Our stereochemical studies on the alkynol (−)-12 and the enyne (+)-7 confirm that Ryu and Hatakeyama’s (3S)-stereochemical revision of (+)-inthomycin C is invalid and that Zeeck and Taylor’s original (3R)-stereostructure for (+)-inthomycin C is correct.",
author = "Hale, {Karl J.} and Milosz Grabski and Soraya Manaviazar and Maciej Maczka",
year = "2014",
doi = "10.1021/ol5000499",
language = "English",
volume = "16",
pages = "1164--1167",
journal = "Organic Letters",
issn = "1523-7060",
publisher = "American Chemical Society",
number = "4",

}

TY - JOUR

T1 - Asymmetric Total Synthesis of (+)-Inthomycin C Via O-Directed Free Radical Alkyne Hydrostannation with Ph3SnH and Catalytic Et3B: Reinstatement of the Zeeck-Taylor (3R)-Structure for (+)-Inthomycin C

AU - Hale, Karl J.

AU - Grabski, Milosz

AU - Manaviazar, Soraya

AU - Maczka, Maciej

PY - 2014

Y1 - 2014

N2 - A new pathway to (+)-inthomycin C is reported that exploits an O-directed free radical hydrostannation reaction on (−)-12 and a Stille cross-coupling as key steps. Significantly, the latter process was effected on 19 where a gauche-pentane repulsive interaction could interfere. Our stereochemical studies on the alkynol (−)-12 and the enyne (+)-7 confirm that Ryu and Hatakeyama’s (3S)-stereochemical revision of (+)-inthomycin C is invalid and that Zeeck and Taylor’s original (3R)-stereostructure for (+)-inthomycin C is correct.

AB - A new pathway to (+)-inthomycin C is reported that exploits an O-directed free radical hydrostannation reaction on (−)-12 and a Stille cross-coupling as key steps. Significantly, the latter process was effected on 19 where a gauche-pentane repulsive interaction could interfere. Our stereochemical studies on the alkynol (−)-12 and the enyne (+)-7 confirm that Ryu and Hatakeyama’s (3S)-stereochemical revision of (+)-inthomycin C is invalid and that Zeeck and Taylor’s original (3R)-stereostructure for (+)-inthomycin C is correct.

U2 - 10.1021/ol5000499

DO - 10.1021/ol5000499

M3 - Letter

VL - 16

SP - 1164

EP - 1167

JO - Organic Letters

JF - Organic Letters

SN - 1523-7060

IS - 4

ER -