Genomic relationships between maize and its wild relatives

Recent molecular studies confirm the long-held theory that maize is a tetraploid, but the identity of the ancestral diploid species remains an enigma. The various hypotheses were investigated using genomic in situ hybridization (GISH). Total genomic DNA from 10 wild relatives of maize were used as probes onto maize chromosomes to see if this could identify the ancestral genome donors in maize. While none of the taxa hybridized to a subset of chromosomes, genomic DNA from Zea mays ssp. mexicana, Z. mays ssp. parviglumis, Z. diploperennis, Tripsacum dactyloides and Coix lacryma-jobi all showed a similar hybridization pattern consisting of a dispersed signal over all maize chromosomes. Moreover, the first four species also showed highly localized subtelomeric signal on the long arms of maize chromosomes 5, 6, 7, and 8. In contrast, three Sorghum species tested (S. bicolor, S. halapense, and S. versicolor) only showed hybridization at the nucleolar organizer region. In light of recent data on retrotransposon occurrence in maize, the results may provide insights into the timing of speciation of Zea, Tripsacum, and Coix. Data obtained from the tetraploid Z. perennis strongly supported its taxonomic separation from the diploid Z. diploperennis.

Additions of enantioenriched allenylzinc and indium reagents to lactic aldehyde ethers

Allenylzinc and indium reagents were generated in situ through Pd(0)-catalyzed metalation of (R)- and (S)-3-butyn-2-ol methanesulfonate with Et(2)Zn and InI. These reagents add to the benzyl and TBS ethers of (S)-lactic aldehyde to afford diastereomeric stereotriads in moderate to high yield. The (S)/(S) combination afforded the anti,anti adducts with 94:6-100:0 diastereoselectivity. The (R)/(S) combination was mismatched, affording a mixture of anti,syn and syn,anti adducts in diastereomeric ratios of ca. 80:20-85:15. Addition of the racemic allenylmetal reagents to the (S)-lactic aldehyde ethers afforded the products of matched and mismatched pairings in equal amount.

Synthesis of beta-hydroxy ketones and vinylsilanes from homopropargylic alcohols by intramolecular hydrosilation

Catalytic intramolecular hydrosilation of nonracemic homopropargylic alcohols affords the corresponding five-membered cyclic siloxanes regiospecifically. Oxidation or alkylmetal addition converts these intermediates into beta-hydroxy ketones or vinylsilanes under mild conditions.