Benjamin H. Rotstein,†,‡ Serge Zaretsky,† Vishal Rai,†,§ and Andrei K. Yudin*,† †Davenport Research Laboratories, Department of Chemistry, University of Toronto, 80 St. George Street, Toronto, Ontario Canada, M5S 3H6 ‡Division of Nuclear Medicine and Molecular Imaging, Massachusetts General Hospital, and Department of Radiology, Harvard Medical School, 55 Fruit Street, Boston, Massachusetts 02114, United States Department of Chemistry, Indian Institute of Science Education and Research (IISER) Bhopal, Indore By-pass Road, Bhauri, Bhopal 462 066, MP India

Small Heterocycles in Multicomponent Reactions

In a previous review it was predicted that "the reactivity of five-coordinate complexes would certainly be different than that of the four-coordinate derivatives". Structurally and spectroscopically, there is very little difference in the higher-coordinate compounds when compared to the four-coordinate derivatives. However, the prediction was remarkably accurate, if not a bit understated, for the reactivity of these compounds. There appears to be a tremendous potential in catalysis and synthesis for the five-coordinate derivatives, far more possibilities than exist for the lower-coordinate derivatives. Furthermore, the higher-coordinate derivatives are rarely air or moisture sensitive and, thus, may be handled under a wider range of conditions. Although reactions such as oxirane and lactide polymerizations are fairly well-known now with five- and six-coordinate aluminum compounds, the potential of these compounds has only begun to be developed. It is easy to imagine that these types of compounds will see wider use than the related transition-metal compounds.

Group 13 compounds incorporating Salen ligands.

Asymmetric aminocatalysis exploits the potential of chiral primary and secondary amines to catalyze asymmetric reactions. It has greatly simplified the functionalization of carbonyl compounds while ensuring high enantioselectivity. Recent advances in cinchona-based primary amine catalysis have provided new synthetic opportunities and conceptual perspectives for successfully attacking major challenges in carbonyl compound chemistry, which traditional approaches have not been able to address. This Review outlines the historical context for the development of this catalyst class while charting the landmark discoveries and applications that have further expanded the synthetic potential of aminocatalysis.

Cinchona-based primary amine catalysis in the asymmetric functionalization of carbonyl compounds.

When asymmetric aminocatalysis meets the vinylogy principle

Cooperative Organocatalysis for the Asymmetric γ Alkylation of α‐Branched Enals

Conceptually New Directed Aldol Condensation Using Aluminum Tris(2,6-diphenylphenoxide)

Background Japan Clinical Oncology Group (JCOG) 0212 (ClinicalTrials.gov NCT00190541) was a non-inferiority phase III trial of patients with clinical stage II-III rectal cancer without lateral pelvic lymph node enlargement. The trial compared mesorectal excision (ME) with ME and lateral lymph node dissection (LLND), with a primary endpoint of recurrence-free survival (RFS). The planned primary analysis at 5 years failed to confirm the non-inferiority of ME alone compared with ME and LLND. The present study aimed to compare ME alone and ME with LLND using long-term follow-up data from JCOG0212. Methods Patients with clinical stage II-III rectal cancer below the peritoneal reflection and no lateral pelvic lymph node enlargement were included in this study. After surgeons confirmed R0 resection by ME, patients were randomized to receive ME alone or ME with LLND. The primary endpoint was RFS. Results A total of 701 patients from 33 institutions were assigned to ME with LLND (351) or ME alone (350) between June 2003 and August 2010. The 7-year RFS rate was 71.1 per cent for ME with LLND and 70·7 per cent for ME alone (hazard ratio (HR) 1·09, 95 per cent c.i. 0·84 to 1·42; non-inferiority P = 0·064). Subgroup analysis showed improved RFS among patients with clinical stage III disease who underwent ME with LLND compared with ME alone (HR 1·49, 1·02 to 2·17). Conclusion Long-term follow-up data did not support the non-inferiority of ME alone compared with ME and LLND. ME with LLND is recommended for patients with clinical stage III disease, whereas LLND could be omitted in those with clinical stage II tumours.

Long-term follow-up of the randomized trial of mesorectal excision with or without lateral lymph node dissection in rectal cancer (JCOG0212)

The combined use of aluminum tris(2,6-diphenylphenoxide) (ATPH) and lithium 2,2,6,6-tetramethylpiperidide (LTMP) has proven to be effective for the mixed crossed aldol condensation between conjugated esters and various aldehydes. An example is shown in Equation (1).

Mixed Crossed Aldol Condensation between Conjugated Esters and Aldehydes Using Aluminum Tris(2,6-diphenylphenoxide).

Molecular Recognition of Carbonyl Compounds Using Aluminum Tris(2,6-diphenylphenoxide) (ATPH): New Regio- and Stereoselective Alkylation of α,β-Unsaturated Carbonyl Compounds

Masahito Shiozawa

Papers

Conceptually New Directed Aldol Condensation Using Aluminum Tris(2,6-diphenylphenoxide)

Long-term follow-up of the randomized trial of mesorectal excision with or without lateral lymph node dissection in rectal cancer (JCOG0212)

Mixed Crossed Aldol Condensation between Conjugated Esters and Aldehydes Using Aluminum Tris(2,6-diphenylphenoxide).

Molecular Recognition of Carbonyl Compounds Using Aluminum Tris(2,6-diphenylphenoxide) (ATPH): New Regio- and Stereoselective Alkylation of α,β-Unsaturated Carbonyl Compounds

Gemischte Aldol-Kreuzkondensation zwischen konjugierten Estern und Aldehyden mit Aluminiumtris(2,6-diphenylphenoxid)