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A general one-pot method for the enantioselective synthesis of β,β-disubstituted allylic alcohols has been developed starting from readily available terminal alkynes and aldehydes. Trisubstituted (E)-vinylaluminium reagents, generated regio- and stereoselectively by the Zr-catalyzed carboalumination of the alkynes with Me3Al, was used in subsequent enantioselective addition reactions with aldehydes using a DPP-H8-BINOL-derived titanium catalyst system at low catalyst loading (5 mol-%).

A general one-pot method for the enantioselective synthesis of β,β-disubstituted allylic alcohols has been developed starting from readily available terminal alkynes and aldehydes. Trisubstituted (E)-vinylaluminium reagents, generated regio- and stereoselectively by the Zr-catalyzed carboalumination of the alkynes with Me3Al, was used in subsequent enantioselective addition reactions with aldehydes using a DPP-H8-BINOL-derived titanium catalyst system at low catalyst loading (5 mol-%).

Background and Objectives The presence of lymph node (LN) metastases is an important prognostic factor in patients with biliary cancers. The aim of this study was to characterize systematically the morphological features of metastatic LNs in biliary cancers. Methods Four hundred ninety-six LNs (including 112 para-aortic LNs) dissected from 47 patients with biliary cancer were examined. The diameter of the long axis (size) and the percent metastatic area relative to whole-node area were measured from histologic specimens. Results The average size of metastatic LNs (9.5 mm) was significantly larger than those without metastasis (6.5 mm; P 7.5 mm, but the sensitivity of this predictor of metastasis was low (60.8%). In general, metastatic area correlated significantly with the size of metastatic LNs (P = 0.023). Para-aortic LNs contained metastasis in 7.1% of cases, and only 25% of para-aortic LNs with a high ratio of metastatic area could be evaluated from preoperative CT scans. Although large LNs are highly suggestive of metastasis, poor detection of many small LNs with a low percentage of metastatic area can increase risk in patients with biliary tract cancer. J. Surg. Oncol. 2008;97:423–427. © 2008 Wiley-Liss, Inc. Although large LNs are highly suggestive of metastasis, poor detection of many small LNs with a low percentage of metastatic area can increase risk in patients with biliary tract cancer. J. Surg. Oncol. © 2008 Wiley-Liss, Inc.