Anthony C. Waiss

Simmondsin, an unusual 2-cyanomethylenecyclohexyl glucoside from Simmondsia californica

Simmondsin, a monoglucoside extracted from seeds of the jojoba plant (Simmondsia californica), has been shown to be 2-(cyanomethylene)-3-hydroxy-4,5-dimethoxycyclohexyl β-D-glucoside (1). Analysis of the n.m.r. spectra of this compound and its penta-acetate permits assignment of the stereochemistry as well as establishing the point of attachment of the glucose.

Ergostanoids from Petunia parodii

Abstract Leaves of Petunia parodii gave three new petuniolides, one of which has a 9,11-double bond. Of the other two, one has a 9β-OH with an 11,12-double bond and the second has a 9β, 19-cyclopropyl system as well as an 11β-OH and a 12-keto group. Also present are six new petuniasterones which arise from rearrangement of the D-ring epoxides, petuniasterones K and L. A 13,17- seco -petuniasterone was also present.

Egostanoids from Petunia inflata

Abstract Leaves of Petunia inflata gave the following new steroids: (22 R , 24 S )-1α-acetoxy-24, 25-epoxy-7α-hydroxy-22-nicotinoyloxyergost-4-en-3-one (petuniasterone B 22-nicotinate), (22 R , 24 S )-1α-acetoxy-7α,22-dinicotinoyloxy-24, 25-epoxyergost-4-en-3-one (petuniasterone B 7, 22-dinicotinate), (22 R , 24 S )-7α,22-diacetoxy-24, 25-epoxyergosta- 1, 4-dien-3-one (petuniasterone C 7,22-diacetate), (22 R , 24 S )-24, 25-epoxy-7α-hydroxy-22-nicotinoyloxyergosta-1, 4-dien-3-one (petuniasterone C 22-nicotinate), (22 R , 24 S )-7α-acetoxy-24,25-epoxy-22-nicotinoyloxyergosta-1, 4-dien-3-one (petuniasterone C 7-acetate-22-nicotinate), (22 R , 24 S )-7α, 22-dinicotinoyloxy-24, 25-epoxyergosta-1,4-dien-3-one (petuniasterone C 7, 22-dinicotinate), (22 R , 24 R )-1α-acetoxy-7α,22,24,25-tetrahydroxyergost-4-en-3-one 22,24,25-orthoacetate (petuniasterone S), (22 R , 24 R )-1α-acetoxy-7α,22,24,25-tetrahydroxyergost-4-en-3-one 22,24,25-orthonicotinate (petunianine C). Those compounds having 1α-acetoxy groups are easily converted into the A-ring dienones by mild base. Orthoester and other side chain derivatives may be formed from the 24, 25-epoxides upon acid treatment.

Petuniasterones, novel ergostane-type steroids of Petunia hybridia Vilm. (Solanaceae) having insect-inhibitory activity. X-ray molecular structure of the 22,24,25-[(methoxycarbonyl)orthoacetate] of 7α,22,24,25-tetrahydroxy ergosta-1,4-dien-3-one and of 1α-acetoxy-24,25-epoxy-7α-hydroxy-22-(methylthiocarbonyl)acetoxyergost-4-en-3-one

Three new types of ergostanoids with unusual functionalities were isolated from leaves and stems of Petunia hybrids. These include the [(methylthio)carbonyl]orthoacetate of (22R,24R)-7α,22,24,25-tetrahydroxyergosta-1,4-dien-3-one (1) and the respective [(methylthio)carbonyl]acetates, acetates, and free 22-alcohols derived from (22R,24S)-1α-acetoxy-24,25-epoxy-7α,22-dihydroxyergosta-4-en-3-one [(3), (4), and (5)] and (22R,24S)-24,25-epoxy-7α,22-dihydroxyergosta-1,4-dien-3-one [(6), (7), and (8)]. Structures of compounds (2) and (3) were determined by X-ray crystallography. Compound (1) reduced the growth of Heliothis zea larvae to 50% of control values at ca. 40 p.p.m. in artificial diets.

Petuniolides. Unusual ergostanoid lactones from Petunia species that inhibit insect development.

Four new compounds that strongly contribute to the resistance of Petunia parodii and P. integrifolia against feeding by larvae of the lepidopteran, Heliothis zea, were isolated from leaves of these plant species. These consist of the (22R,24R)-22,24,25-orthoacetates and orthopropionates derived from multiply functionalized ergostanoids in which the A-ring has lost one carbon and has been converted into a spirolactone. An epoxy group is present at position 6α,7α. Petuniolides A (11) and B (12) have a Δ9(11)-12α-acetoxy group whereas petuniolides C (13) and D (14) possess the corresponding allylic ketone functionality. The molecular structures of (12) and (14) were determined by X-ray crystallography.

Petuniasterones. Part 2. Novel ergostane-type steroids from Petunia hybrida vilm. (solanaceae)

Four new compounds in the petuniasterone series were isolated from leaves and stems of Petunia hybrida. These all possess the Δ1,4-diene-3-one structure and have a 7α-oxygenated functionality. Compounds identified include the 17β-hydroxy derivative of petuniasterone A (9) and its 7-acetate (10) in addition to petuniasterone D (3), which is the orthoacetate of (22R,24R)-7α-22,24,25-tetrahydroxyergosta-1,4-dien-3-one as well as 12α-acetoxypetuniasterone D 7-acetate (5).

Petunianines, unusual steroidal nitrogenous bases from Petunia inflata

The structures and stereochemistry of two ergostanoids from Petunia inflata, bearing pyridine rings on the side chain, have been established by spectroscopy and X-ray crystallographic analysis.