Asymmetric Total Synthesis of ent-PyripyropeneA

作者：Fuse Shinichiro^*; Ikebe Ayako; Oosumi Kazuya; Karasawa Tomoya; Matsumura Keisuke; Izumikawa Miho; Johmoto Kohei; Uekusa Hidehiro; Shin ya Kazuo; Doi Takayuki; Takahashi Takashi

来源：Chemistry - A European Journal, 2015, 21(26): 9454-9460.

DOI：10.1002/chem.201500703

• insecticidal activity
• meroterpenoids
• natural products
• radical reactions
• titanium

An asymmetric total synthesis of ent-pyripyropeneA was achieved by a convergent synthetic route. We used our originally developed Ti-III-catalyzed radical cyclization to construct an AB-ring portion that consisted of a trans-decalin skeleton with five contiguous stereogenic centers. The coupling between the AB-ring and the DE-ring portions, and a subsequent C-ring cyclization, led to the total synthesis of ent-pyripyropeneA. An evaluation of the insecticidal activity of ent-pyripyropeneA against two aphid species revealed that ent-pyripyropeneA was 35-175 times less active than naturally occurring pyripyropeneA. This result indicated that the biological target of pyripyropeneA recognizes the absolute configuration of pyripyropeneA.

• 出版日期2015-6-22