TheA rmillariaa nd Lactariusg enerao ff ungi producet he antimicrobiala nd cytotoxicm ellolide,p rotoilludane,a nd marasmanes esquiterpenoids. We report au nified synthetics trategyt oa ccesst he protoilludane, mellolide, and marasmanef amilieso fn atural products.T he keyf eatureso f theses yntheses are1 )the organocatalytic, enantioselective construction of keyc hirali ntermediates from as implea chiral precursor,2 )the utilityo fakey1 ,2-cyclobutanediol intermediatetoserve as aprecursor to each naturalproduct class, and3)a direct chemical conversion of ap rotoilludane to am arasmane throughs erendipitous ring contraction, whichp rovidese xperimentalsupport fortheir proposed biosynthetic relationships. Scheme 1. Overall synthesis plan. Supportinginformation (including experimental details) and the ORCID identification number(s) for the author(s) of this article can be found under: https://doi.org/10.1002/anie.201705308. Angewandte Chemie Communications 9864 2017 Wiley-VCH Verlag GmbH &C o. KGaA, Weinheim Angew.C hem.I nt. Ed. 2017, 56,9 864 -9867 Scheme 2. Exploration of the NHC-catalyzed annulation strategy.D MS = dimethylsulfide, DIBAL-H = diisobutylaluminium hydride, DMP = Dess-Martin periodinane, PPA = polyphosphoric acid, DBU = 1,8-diazabicyclo(5.4.0)undec-7ene, LiHDMS = lithium bis(trimethylsilyl)amide, Tf = triflate. Angewandte Chemie Communications 9865