Trichodermaerin: a diterpene lactone fromTrichoderma asperellum

Abstract

The title compound, C20H28O3, known as ‘trichodermaerin’ [systematic name: (4E)-4,9,15,16,16-penta­methyl-6-oxa­tetra­cyclo­[10.3.1.01,10.05,9]hexa­dec-4-ene-7,13-dione], is a diterpene lactone which was isolated from Trichoderma asperellum. The structure has a tetra­cycic 6–5–7–5 ring system, with the cyclo­hexa­none ring adopting a twisted half-chair conformation and the cyclo­pentane ring adopting a half-chair conformation, whereas the cyclo­heptene and tetra­hydro­furan­anone rings are in chair and envelope (with the methyl-substituted C atom as the flap) conformations, respectively. The three-dimensional architecture is stabilized by C—H⋯O inter­actions.

Non-Volatile Metabolites from Trichoderma spp.

“…Nine compounds were isolated from the fungus T. asperellum : trichodermaerin ( 8 ) [5]; 6-amyl alpha-pyrone ( 9 ) [6]; aspereline G ( 10 ); aspereline H ( 11 ); aspereline A ( 12 ); aspereline C ( 13 ); aspereline D ( 14 ); aspereline E ( 15 ); and aspereline F ( 16 ) [7]. Among them, compounds 10 and 11 were two new peptaibols.…”

Trichoderma species from plant and soil: An excellent resource for biosynthesis of terpenoids with versatile bioactivities

“… [90] , [91] 205 harzianone Trichoderma longibrachiatum. [91] 206 trichodermaerin Trichoderma erinaceum ; Trichoderma asperellum [92] , [93] 207 (9 R ,10 R )-dihydro-harzianone Trichoderma sp. Xy24 [94] 208 harzianelactone Trichoderma sp.…”

“…Later, isoharziandione ( 2 0 4 ) was obtained as 3,7,11,15,15-pentamethyl tetracyclo [3–2–1–04–12–5–2–08–11]tetradec-7-en-1–10 dione in 1997 [90] , but was subsequently revised to harziandione ( 2 0 3 ) on the basis of 13 C NMR data comparison and calculation in 2012 by Miao et al and they also got another novel congener harzianone ( 2 0 5 ), from T. longibrachiatum [91] . Afterwards, trichodermaerin ( 2 0 6 ), a novel diterpenoid lactone with a tetracyclic 5/7/5/6 ring system, was isolated both from T. erinaceum in 2013 [92] and from T. asperellum in 2014 [93] , which represents a sub-type with the typical 4-membered cyclobutanone ring varied to a 5-membered lactone ring, also including harzianelactone ( 2 0 8 ) [94] , harzianelactones A and B ( 212 , 213 ) [95] and 3 S -hydroxytrichodermaerin ( 2 2 9 ) [100] . And methyl 3 S -hydroxy-10,11-seco-harzianate ( 2 3 0 ) was the first example with the cyclobutanone ring cleaved [100] , while the other analogues differ mainly in the configuration and substitution on the basic skeleton, including (9 R ,10 R )-dihydro-harzianone ( 2 0 7 ) [94] , 11-hydroxy-9-harzien-3-one ( 2 0 9 ) [39] , 3 R -hydroxy-9 R ,10 R -dihydroharzianone ( 2 1 0 ) [40] , 3 S -hydroxyharzianone ( 2 1 1 ) [47] , harzianones A–D ( 214 – 217 ), harziane ( 2 1 8 ) [95] , koninginol C ( 2 1 9 ) [50] , harzianone E ( 2 2 0 ) [43] , deoxytrichodermaerin ( 2 2 1 ) [96] , harzianol A ( 2 2 2 ) [97] , [99] , harzianols F-O ( 223 – 227 , 231 – 235 ) [98] , [99] , and 3 S -hydroxy-9 R ,10 R -dihydroharzianone ( 2 2 8 ) [100] .…”

Harzianone Biosynthesis by the Biocontrol Fungus Trichoderma

“…[8c, d, 9] Av olatile sesquiterpene alcohol that is frequently released by Trichoderma is tricho-acorenol (3), which was first identified from culture extractso fTrichoderma koningii. [12] Furthermore, a series of structurally unique and biosynthetically related diterpenes represented by harzianone (4), [13] harziandione (5) [14] and trichodermaerin (6) [15] were isolated from Trichoderma. [12] Furthermore, a series of structurally unique and biosynthetically related diterpenes represented by harzianone (4), [13] harziandione (5) [14] and trichodermaerin (6) [15] were isolated from Trichoderma.…”