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Biomedical subjects

Thomas Wynn

Publications and source records attributed to Thomas Wynn.

6 recordsLinked to original sources
PubMed2005

Lewis base activation of Lewis acids: catalytic, enantioselective addition of silyl ketene acetals to aldehydes.

The concept of Lewis base activation of Lewis acids has been reduced to practice for catalysis of the aldol reaction of silyl ketene acetals and silyl dienol ethers with aldehydes. The weakly acidic species, silicon tetrachloride (SiCl4), can be activated by binding of a strongly Lewis basic chiral phosphoramide, leading to in situ formation of a chiral Lewis acid. This species has proven to be a competent catalyst for the aldol addition of acetate-, propanoate-, and isobutyrate-derived silyl ketene acetals to conjugated and nonconjugated aldehydes. Furthermore, vinylogous aldol reactions of silyl dienol ethers are also demonstrated. The high levels of regio-, anti diastereo-, and enantioselectivity observed in these reactions can be rationalized through consideration of an open transition structure where steric interactions between the silyl cation complex and the approaching nucleophile are dominant.

Journal Article↗
PubMed2004

The expert Neandertal mind.

Cognitive neuropsychology, cognitive anthropology, and cognitive archaeology are combined to yield a picture of Neandertal cognition in which expert performance via long-term working memory is the centerpiece of problem solving. This component of Neandertal cognition appears to have been modern in scope. However, Neandertals' working memory capacity, which is the ability to hold a variety of information in active attention, may not have been as large as that of modern humans. This characteristic helps us understand features of the archaeological record, such as the rarity of innovation, and allows us to make empirically based speculations about Neandertal personality.

Animals↗
PubMed2002

Lewis base activation of lewis acids. Addition of silyl ketene acetals to aldehydes.

The weak Lewis acid silicon tetrachloride can be activated by catalytic amounts of the chiral bisphosphoramide (R,R)-3 to form a highly reactive, chiral trichlorosilyl cation which is an extremely effective promoter of aldol addition reactions between aldehydes and silyl ketene acetals. The tert-butyldimethylsilyl ketene acetal of methyl acetate adds nearly instantaneously to aromatic and olefinic aldehydes as well as aliphatic aldehydes (albeit more slowly) with excellent enantioselectivity. The homologous tert-butyldimethylsilyl ketene acetal of tert-butyl propanoate adds with nearly exclusive anti diastereoselectivity to a similar range of aldehydes also with excellent enantioselectivity. The origin of the slower reaction rate with aliphatic aldehydes is revealed to be the formation of chlorosilyl ether adducts.

Journal Article↗
PubMed2002

Archaeology and cognitive evolution.

Archaeology can provide two bodies of information relevant to the understanding of the evolution of human cognition--the timing of developments, and the evolutionary context of these developments. The challenge is methodological. Archaeology must document attributes that have direct implications for underlying cognitive mechanisms. One example of such a cognitive archaeology is found in spatial cognition. The archaeological record documents an evolutionary sequence that begins with ape-equivalent spatial abilities 2.5 million years ago and ends with the appearance of modern abilities in the still remote past of 400,000 years ago. The timing of these developments reveals two major episodes in the evolution in spatial ability, one, 1.5 million years ago and the other, one million years later. The two episodes of development in spatial cognition had very different evolutionary contexts. The first was associated with the shift to an open country adaptive niche that occurred early in the time range of Homo erectus. The second was associated with no clear adaptive shift, though it does appear to have coincided with the invasion of more hostile environments and the appearance of systematic hunting of large mammals. Neither, however, occurred in a context of modern hunting and gathering.

Animals↗