Total syntheses of seminolipid and its analogues by using 2,6-bis(trifluoromethyl)phenylboronic acid as protective reagent.

A concise total synthesis of seminolipid, a sulfoglycolipid, has been achieved; key features include regioselective, tin-free sulfation of allyl ß-d-galactopyranoside using 2,6-bis(trifluoromethyl)phenylboronic acid as protective reagent, stereoselective epoxidation, and site-selective acylation. The utility of this divergent synthetic approach to introduce 2,2,2-trichloroethyl-protected sulfate group at an early stage without toxic and environmentally unfavorable tin reagents was demonstrated by the syntheses of three seminolipid analogues with different side-chains from the common intermediate.

[A Curatively Resected Case of Lateral Lymph Node Metastasis Five-Years after Initial Surgery for Rectal Cancer].

A 74-year-old male had undergone laparoscopic abdominoperineal resection for lower rectal cancer in July 2009. The pathological diagnosis was T2, N0, M0, pStage I (TNM 7th). Because of pathological venous invasion, adjuvant chemotherapy with Tegafur-uracil(UFT)plus Leucovorin for a year was performed. A CT examination revealed slowly growing peripheral right internal iliaclymph node. PET-CT demonstrated a 20mm right lateral lymph node(LLN)metastasis without other distant metastases. On diagnosis of solitary LLN metastasis of rectal cancer, the patient underwent surgical lymph node resection in September 2014. The pathological diagnosis was lymph node metastasis from rectal cancer. Subsequently, the patient received mFOLFOX6 adjuvant chemotherapy for 6 months. The patient remains alive without any recurrence 31 months after the second surgical treatment. lt is important to consider that LLN metastasis of Stage I rectal cancer might still occur a long time after the curative operation.

A case of an intramesenteric GIST accurately diagnosed and completely resected by PET-CT and laparoscopy after gastrectomy for gastric cancer.

We performed the accurate diagnosis and complete surgical resection of a gastrointestinal stromal tumor at the mesentery of the small bowel. Computed tomography (CT) in a 62-year-old man at 2 years after gastrectomy for gastric cancer showed a mesenteric tumor, with no other tumors noted. Positron emission tomography-computed tomography (PET-CT) showed a maximum standardized uptake value (SUV max) of 2.9 at the tumor. The presence of a single and low SUV max tumor allowed us to perform laparoscopic surgery. Partial resection of the tumor with an adequate margin was performed. The pathological findings showed c-kit positivity and a low Ki-67 proliferation index (<5%). In the present case, PET-CT and laparoscopic assessments were useful for accurately evaluating the surgical resectability of the mesenteric tumor after distal gastrectomy for gastric cancer. The low SUV max and laparoscopic findings led to complete surgical resection of a mesenteric tumor.

2,6-Bis(trifluoromethyl)phenylboronic Esters as Protective Groups for Diols: A Protection/Deprotection Protocol for Use under Mild Conditions.

The application of 2,6-bis(trifluoromethyl)phenyl boronic acid ( o-FXylB(OH)2; o-FXyl = 2,6-(CF3)2C6H3) as a recoverable and reusable protective agent for diols is described. The resulting cyclic boronic esters are water- and air-stable and tolerant to various organic transformations. Moreover, they can be deprotected under mild conditions. This methodology was applied to the synthesis of a highly conjugated enetriyne natural product with anti-angiogenic activities.