A homochiral microporous hydrogen-bonded organic framework (HOF-2) based on a BINOL derivative has been synthesized and structurally characterized to be a uninodal 6-connected {3(3)5(5)6(6)7} network. This new HOF exhibits not only a permanent porosity with the BET of 237.6 m(2) g(-1) but also, more importantly, a highly enantioselective separation of chiral secondary alcohols with ee value up to 92% for 1-phenylethanol.

Four porous isostructural mixed-metal-organic frameworks (M'MOFs) have been synthesized and structurally characterized. The pores within these M'MOFs are systematically tuned by the interplay of both the metalloligands and organic ligands which have enabled us not only to direct their highly selective separation of chiral alcohols 1-phenylethanol (PEA), 2-butanol (BUT), and 2-pentanol (2-PEN) with the highest ee up to 82.4% but also to lead highly selective separation of achiral C(2)H(2)/C(2)H(4) separation. The potential application of these M'MOFs for the fixed bed pressure swing adsorption (PSA) separation of C(2)H(2)/C(2)H(4) has been further examined and compared by the transient breakthrough simulations in which the purity requirement of 40 ppm in the outlet gas can be readily fulfilled by the fixed bed M'MOF-4a adsorber at ambient conditions.

Because the biological and/or pharmacologicalp roperties of ag iven molecule often depend on the absolutea nd relative configurations of the stereogenic centers,d ifferent diastereomers may exhibit totally different biological and/or pharmacological activities.T herefore,f or compoundsc ontaining multiple stereogenic centers,t he stereoselective asymmetric synthesis of all of the individual diastereomers, preferably using ac atalytic method, is of great interest andi mportance in organic synthesis and drug discovery.I nt his context, the development of catalytic diastereodivergent methods is highly desirable,s incei tp rovides one of the most efficient ways to access multipled iastereomers from the same substrates.T he current review attemptst os umma-rize the developments in the field of asymmetric diastereodivergent catalysis. Scheme 5. Michaelr eactions for the synthesis of both syn-and anti-diastereomers. Scheme 6. Diastereodivergent tandem Michael-Michael reaction. Scheme 8. Diastereodivergent aldol reactionsofc ycloketones andaryl aldehydes. Scheme 9. l-Proline/guanidinium salt co-catalyzed diastereodivergent aldol reactions. Scheme 7. Diastereodivergent synthesis of 2,4-dinitro ester derivatives using bifunctional squaramidec atalysts. Scheme 11. Diastereodivergent synthesis of spirooxindole derivatives.Scheme 12. Diastereodivergent synthesis of bis(spirocyclic)oxindoles derivatives. Scheme 14. Diastereodivergent formal hydroaminination, hydrooxidation, and reductive Mannich reaction of enal 52. Scheme 15. Diastereodivergent alkylamination, diamination, and aminooxidation of enal 64. Scheme 16. Generation of diastereodivergence in the one-pot sequential cycle-specific catalysis. Scheme 17. Organocatalytic diastereodivergent synthesis of furan-fused carbocycles. Scheme 18. Accesstot he full matrixo fthe stereoisomers of the annulated furan. Scheme 19. Diastereodivergent cascade reaction towards chiral diamine derivatives. Scheme 23. Diastereodivergent synthesis of indolo[2,3-a]-, benzo[a]-, and thieno[3,2-a]quinolizidine skeletons. Scheme 24. Diastereodivergent [4+ +2] cycloaddition of cyclic enones with alkenyl-or alkynylmethylidenemalononitriles. Scheme 25. Diastereodivergent synthesis of cyclohexane derivativesu sing bifunctional squaramide catalysts. Scheme 26. Diastereodivergent synthesis of polyfuntionalized cyclohexanes using MDOs. Scheme 27. Enantioselectived iastereodivergentsynthesis of lycorane diastereomers using MDOs. Scheme 28. Diastereodivergent tandem hetero-Diels-Alder/oxa-Michael reaction catalyzed by MDOs. Scheme 29. Diastereodivergent approach towards dihydrobezofuran derivatives. Scheme 30. Diastereodivergent approach towards tetrahydrofuran derivatives. Scheme 31. Proposed transition states leading to cis-a nd trans-dihydrobenzofuran derivatives. Scheme 32. Adiastereodivergent[4 + +2] annulation of 16 and 127. Scheme 35. Diastereodivergent cycloaddition of azomethine ylides with C 60 . Scheme 36. Diastereodivergent synthesis of the four stereoisomers of the pyrrolidinoendofullerenes. S...

Sustainability in chemical synthesis is a major aspect of the current synthetic endeavors and, therefore,m imicking the biological process in the laboratory nowadays has the highest priority.T owards achieving this goal, designingorganic reactions in domino mode rathert han the multistep synthetic pathways andu sing organocatalysisi nstead of metal catalysis have received al ot of attention due to the inherenta dvantageso ft hese processes in terms of synthetic efficiencya nd sustainability.A saresult, the field of asymmetric organocatalytic domino reactions has witnessed tremendous progress in recent years.T his review attempts to summarize the latest developments in asymmetric organocatalyzed domino reactions since 2012, with the emphasis on the catalysts andr eactionm odes.D iscussions on the reactionm echanismsa nd the applications of the developed domino reactionm ethodsi nt he synthesis of biologically active molecules and natural products are also includedwhen appropriate.

[reaction: see text] The catalytic activity of the prolinamide-type catalysts may be improved by introducing additional prolinamide moiety into the catalyst, while the enantioselectivity can still be maintained or further improved. A C2-symmetric bisprolinamide with two prolinamide moieties has been found to be an excellent catalyst for direct aldol reaction with more than doubled reactivity and better asymmetric induction than its monoprolinamide counterpart.