Total Synthesis of Isodaphlongamine H by Iridium‐Catalyzed Reductive [3 + 2] Cycloaddition of <i>N‐</i> Hydroxylactam

S Sora Iwamoto (Department of Applied Chemistry Faculty of Science and Technology Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama Kanagawa 223–8522 Japan) R Reki Nakano (Department of Applied Chemistry Faculty of Science and Technology Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama Kanagawa 223–8522 Japan) K Keiji Sasaki (Department of Applied Chemistry Faculty of Science and Technology Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama Kanagawa 223–8522 Japan) S Shoichiro Kobayashi (Department of Applied Chemistry Faculty of Science and Technology Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama Kanagawa 223–8522 Japan) Y Yuki Taira (Department of Applied Chemistry Faculty of Science and Technology Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama Kanagawa 223–8522 Japan) K Koya Takei (Department of Applied Chemistry Faculty of Science and Technology Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama Kanagawa 223–8522 Japan) R Reiji Kawakita (Department of Applied Chemistry Faculty of Science and Technology Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama Kanagawa 223–8522 Japan) A Ayako Tokuyama (Department of Applied Chemistry Faculty of Science and Technology Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama Kanagawa 223–8522 Japan) H Haruto Nakamura (Department of Applied Chemistry Faculty of Science and Technology Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama Kanagawa 223–8522 Japan) M Manato Tomoike (Department of Applied Chemistry Faculty of Science and Technology Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama Kanagawa 223–8522 Japan) R Ryota Kawahara (Department of Applied Chemistry Faculty of Science and Technology Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama Kanagawa 223–8522 Japan) A Akari Murase (Department of Applied Chemistry Faculty of Science and Technology Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama Kanagawa 223–8522 Japan) S Siro Simizu N Noritaka Chida (Department of Applied Chemistry Faculty of Science and Technology Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama Kanagawa 223–8522 Japan) T Toshitaka Okamura (Department of Applied Chemistry Faculty of Science and Technology Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama Kanagawa 223–8522 Japan) T Takaaki Sato (Department of Applied Chemistry Faculty of Science and Technology Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama Kanagawa 223–8522 Japan)

Abstract

Abstract The total synthesis of isodaphlongamine H based on a lactam strategy, which enables quick access to complex cyclic amines, is described. The strategy begins with alkylation of a chiral lactam and subsequent N ‐oxidation via an imino ether to afford the N ‐hydroxylactam. For the key transformation to functionalize the amide carbonyl, an iridium‐catalyzed reductive [3 + 2] cycloaddition of the N ‐hydroxylactam provides a tricyclic isoxazolidine in a one‐pot process. After the coupling reaction with an allylic silane fragment, the total synthesis is accomplished through intramolecular Hosomi–Sakurai allylation to construct a pentacyclic core. The deoxygenated pentacyclic intermediate shows higher cytotoxicity against HeLa and U937 cell lines than isodaphlongamine H, and might become a lead compound for further biological study.

Article Details

Volume / Issue Vol. 64, Issue 29
Published July 14, 2025
ISSN 1433-7851
Publisher Wiley

Journal Info

Angewandte Chemie International Edition

Wiley

ISSN: 1433-7851 Physical Sciences

Authors (16)

S

Sora Iwamoto

Department of Applied Chemistry Faculty of Science and Technology Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama Kanagawa 223–8522 Japan

R

Reki Nakano

Department of Applied Chemistry Faculty of Science and Technology Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama Kanagawa 223–8522 Japan

K

Keiji Sasaki

Department of Applied Chemistry Faculty of Science and Technology Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama Kanagawa 223–8522 Japan

S

Shoichiro Kobayashi

Department of Applied Chemistry Faculty of Science and Technology Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama Kanagawa 223–8522 Japan

Y

Yuki Taira

Department of Applied Chemistry Faculty of Science and Technology Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama Kanagawa 223–8522 Japan

K

Koya Takei

Department of Applied Chemistry Faculty of Science and Technology Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama Kanagawa 223–8522 Japan

R

Reiji Kawakita

Department of Applied Chemistry Faculty of Science and Technology Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama Kanagawa 223–8522 Japan

A

Ayako Tokuyama

Department of Applied Chemistry Faculty of Science and Technology Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama Kanagawa 223–8522 Japan

H

Haruto Nakamura

Department of Applied Chemistry Faculty of Science and Technology Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama Kanagawa 223–8522 Japan

M

Manato Tomoike

Department of Applied Chemistry Faculty of Science and Technology Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama Kanagawa 223–8522 Japan

R

Ryota Kawahara

Department of Applied Chemistry Faculty of Science and Technology Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama Kanagawa 223–8522 Japan

A

Akari Murase

Department of Applied Chemistry Faculty of Science and Technology Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama Kanagawa 223–8522 Japan

S

Siro Simizu

N

Noritaka Chida

Department of Applied Chemistry Faculty of Science and Technology Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama Kanagawa 223–8522 Japan

T

Toshitaka Okamura

Department of Applied Chemistry Faculty of Science and Technology Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama Kanagawa 223–8522 Japan

T

Takaaki Sato

Department of Applied Chemistry Faculty of Science and Technology Keio University 3‐14‐1 Hiyoshi, Kohoku‐ku Yokohama Kanagawa 223–8522 Japan