Highly efficient protection of alcohols and phenols catalysed by tin porphyrin supported on MIL‐101

Abstract

The catalytic activity of 5,10,15,20-tetrakis(4-aminophenyl)porphyrinatotin(IV) trifluoromethanesulfonate, [Sn IV (TNH 2 PP)(OTf) 2 ], supported on chloromethylated MIL-101, was investigated in the trimethylsilylation of alcohols and phenols with hexamethyldisilazane (HMDS) and also their tetrahydropyranylation with 3,4-dihydro-2H-pyran. Excellent yields, mild reaction conditions, short reaction times and reusability of the catalyst without significant decrease in its initial activity are noteworthy advantages of this supported catalyst.

Oxidation reactions catalysed by molybdenum(VI) complexes grafted on UiO‐66 metal–organic framework as an elegant nanoreactor

“…[15] One of the promising applications of MOFs is for catalysis; MOFs often have catalytic activity on their own, or else they provide ideal supports for catalysts. [16][17][18][19][20][21][22] The organic linkers in the structures of MOFs can be altered by post-synthetic modification (PSM) to produce MOF-based catalysts with improved performance compared to that of the non-supported catalysts. [23] Immobilization on a MOF scaffold is a very powerful tool for heterogenizing soluble inorganic catalysts that combine the benefits of easy separation and recovery of heterogeneous catalysts with the high catalytic activity of soluble transition metal complexes, [24][25][26][27][28][29][30][31][32][33] such as oxomolybdenum species.…”

Catalytic synthesis of cyclic carbonates from epoxides and carbon dioxide by magnetic UiO‐66 under mild conditions

“…Metal–organic frameworks (MOFs), which are metal–oxo clusters linked by tunable organic linkers, have attracted increasing attention because of their porosity, tunable cavities, various topologies and extraordinary surface areas, as well as their numerous potential applications in gas sorption or storage, luminescence, drug release, optoelectronics, chemical sensing and catalysis …”

Graphene oxide‐bound electron‐deficient tin(IV) porphyrin: a highly efficient and selective catalyst for trimethylsilylation of alcohols and phenols with hexamethyldisilazane

“…They used Cr(tpp)Cl for regioselective [3] rearrangement of aliphatic allyl vinyl ethers and for Claisen rearrangement of simple aliphatic allyl vinyl ethers, Fe(tpp)OTf for rearrangement of α,β‐epoxy ketones into 1,2‐diketones and Cr(tpp)OTf for highly regio‐ and stereoselective rearrangement of epoxides to aldehydes . Recently, we have reported the use of tin(IV)tetraphenylporphyrinato perchlorate, tin(IV)tetraphenylporphyrinato trifluoromethanesulfonate, tin(IV)tetraphenylporphyrinato tetrafluoroborate and V(IV)tetraphenylporphyrinato trifluoromethanesulfonate in the ring opening of epoxides, protection of alcohols and phenols, fixation of CO 2 , olefination of aldehydes and cyclopropanation of olefins …”

“…[40][41][42][43] Recently, we have reported the use of tin(IV)tetraphenylporphyrinato perchlorate, tin(IV)tetraphenylporphyrinato trifluoromethanesulfonate, tin (IV)tetraphenylporphyrinato tetrafluoroborate and V(IV) tetraphenylporphyrinato trifluoromethanesulfonate in the ring opening of epoxides, protection of alcohols and phenols, fixation of CO 2 , olefination of aldehydes and cyclopropanation of olefins. [27][28][29][30][31][44][45][46][47][48][49][50][51][52][53][54][55] Graphene, a very recent rising star in materials science, with an atomically thin two-dimensional structure that consists of sp 2 -hybridized carbons, exhibits remarkable electronic and mechanical properties. Functionalization and dispersion of graphene sheets are of crucial importance for their applications.…”

“…By using HMDS, ammonia is produced as a by‐product but the disadvantage of HMDS is its low silylating ability in the absence of a suitable catalyst which increases the reaction times . To enhance the silylating power of HMDS, a variety of catalysts, including trichloroisocyanuric acid, silica‐supported perchloric acid, ZrCl 4 , K‐10 montmorillonite, LiClO 4 , H 3 PW 12 O 40 , iodine, InBr 3 , zirconium sulfophenylphosphonate, CuSO 4 ⋅5H 2 O, sulfonic acid‐functionalized nanoporous silica, MgBr 2 OEt 2 , LaCl 3 , poly( N ‐bromobenzene‐1,3‐disulfonamide) and N , N , N ′, N ′‐tetrabromobenzene‐1,3‐disulfonamide, Fe(TFA) 3 , Fe 3 O 4 , ( n ‐Bu 4 N)Br, ZrO(OTf) 2 , [Sn IV (TNH 2 PP)(OTf) 2 ]/CM‐MIL‐101, [Sn IV (TNH 2 PP)(OTf) 2 ]@CMP, [Sn IV (TPP)(OTf) 2 ], [Sn IV (TPP)(BF 4 ) 2 ], [V IV (TPP)(OTf) 2 ], Ru III (OTf)SalophenCH 2 –NHSiO 2 –Fe and [Ti IV (salophen)(OTf) 2 ], have been reported. Although these procedures provide an improvement, many of these catalysts need long reaction times, severe drastic reaction conditions or tedious workups, are moisture sensitive or are expensive.…”