Synthesis 2020; 52(01): 119-126
DOI: 10.1055/s-0039-1690701
paper
© Georg Thieme Verlag Stuttgart · New York

Rhodium(III)-Catalyzed C–H Activation-Based First Total Synthesis of 6-O-Methyl Anciscochine, an Alkaloid Isolated from Ancistrocladus tectorius

a  Instituto de Química Rosario (IQUIR, CONICET-UNR), 2000 Santa Fe, Argentina   Email: vargas@iquir-conicet.gov.ar   Email: kaufman@iquir-conicet.gov.ar
b  Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario, Suipacha 531, (2000) Rosario, Argentina
,
Brenda S. Romero
b  Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario, Suipacha 531, (2000) Rosario, Argentina
,
a  Instituto de Química Rosario (IQUIR, CONICET-UNR), 2000 Santa Fe, Argentina   Email: vargas@iquir-conicet.gov.ar   Email: kaufman@iquir-conicet.gov.ar
b  Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario, Suipacha 531, (2000) Rosario, Argentina
,
a  Instituto de Química Rosario (IQUIR, CONICET-UNR), 2000 Santa Fe, Argentina   Email: vargas@iquir-conicet.gov.ar   Email: kaufman@iquir-conicet.gov.ar
b  Facultad de Ciencias Bioquímicas y Farmacéuticas, Universidad Nacional de Rosario, Suipacha 531, (2000) Rosario, Argentina
› Author Affiliations
Consejo Nacional de Investigaciones Científicas y Técnicas (CONICET, PUE IQUIR-2016) and Agencia Nacional de Promoción Científica y Tecnológica (ANPCyT, PICT 2017-0149). D.F.V. thanks CONICET for his Doctoral fellowship.
Further Information

Publication History

Received: 28 August 2019

Accepted after revision: 17 September 2019

Publication Date:
10 October 2019 (online)


Abstract

The concise and efficient first total synthesis of 6-O-methyl anciscochine, employing a tandem C–C/C–N formation approach via a rhodium-catalyzed C–H activation/alkenylation/annulation strategy, is reported. This heterocycle was isolated from the liana Ancystrocladus tectorius and features a unique 3-hydroxymethylisoquinoline core that is found in a few other natural products and in some bioactive synthetic compounds. The synthesis, which was executed in four high-yielding steps and a global yield of 43%, involved the oximation of commercial 2,4-dimethoxyacetophenone under CeCl3·7H2O-promotion, followed by pivaloylation of the oxime. A one-pot pivaloxime-directed alkenyl­ation/annulation stage with methyl acrylate, furthered by a NaBH4/ CaCl-mediated reduction of the resulting isoquinoline 3-carboxylate ester completed the sequence.

Supporting Information

 
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