ストラトスフェア・スカベンジャー／リエージェント・レジン選択ガイド

ストラトスフェア・スカベンジャー・レジンは、液相合成や精製工程で使用できるように設計された、官能基導入のポリスチレン樹脂です。スカベンジャー・レジンは、反応工程の最終段階で投入されることにより、導入されている個々の官能基が、副生成物や過剰な試薬との間に十分なイオン的相互作用を生じたり、また非可逆的に共有結合をして、これらの夾雑物除去に使用できます。

ストラトスフェア・リエージェント・レジンは、液相合成で使用される官能基導入のポリスチレン樹脂です。試薬がレジンに固定化されているリエージェント・レジンは、反応工程の初期段階で投入されることにより、液相試薬と同じように合成に使用できます。

ここでは、現在ポリマー・ラボラトリー社が取り揃えています、ストラトスフェア・スカベンジャー／リエージェント・レジンの各製品を、化学構造や各種アプリケーション(推奨反応条件等)などで表にして紹介しました。ここで紹介されているレジンは、ラボ・スケールからキログラム単位のプロセス・スケールまでのバルク供給もできます。

StratoSpheres Synthesis & Purification Guide
Product	Synthetic Utility	Recommended Use
PL-AAEM	Electrophilic Scavenger	Selective scavenging of primary amines and hydrazines.
PL-BH3(CN) MP	Reducing Agent	Reductive amination.
PL-BH4 MP	Reducing Agent	Reduction of carbonyl compounds.
PL-BZA	Nucleophilic Scavenger	Formation of traceless triazine linkers.
PL-CHO	Electrophilic Scavenger	Selective scavenging of primary amines, hydrazines, enolates, and reducing agents.
PL-CO3 MP	Base	Base quenching and scavenging of acids and acidic phenols.
PL-DCC	Coupling Agent	Amide synthesis.
PL-DEAM	Metal Scavenger	Scavenges metals such as Palladium, Titanium, Tin and other Lewis acids. Can also be used to scavenge boronic acids.
PL-DETA	Nucleophilic Scavenger	Scavenges acid chlorides, sulfonyl chlorides and isocyanates.
PL-DIPAM	Tertiary Amine Base	Mesylate formation.
PL-EDA	Nucleophilic Scavenger	Scavenges acid chlorides, sulfonyl chlorides and isocyanates/isothiocyanates.
PL-EDC	Coupling Agent	Amide synthesis.
PL-HCO3 MP	Base	Base quenching, and scavenging of acids and acidic phenols.
PL-HOBt	Activated Ester Reagent	Activated ester formation for amide synthesis and protecting group transfer.
PL-IO4 MP	Oxidizing Agent	Oxidation of alcohols to carbonyls; Cleaves 1,2- diols. Can also be used for sulfur oxidation (sulfoxides and sulfones).
PL-MIA	Electrophilic Scavenger	Scavenges primary and secondary amines.
PL-MPH	Tertiary Amine Base	Scavenges acids generated during condensations.
PL-MPPZ	Tertiary Amine Base	Auxiliary base for in-situ neutralization.
PL-NCO	Electrophilic Scavenger	Scavenges primary and secondary amines, as well as alkoxides, and thiols/thiolates.
PL-PIP	Tertiary Amine Base	Scavenges acids generated during condensations.
PL-PPZ	Nucleophilic Scavenger	High load amine for use in cross coupling reactions and for Fmoc deprotection.
PL-RuO4 MP	Oxidizing Agent	Oxidation of alcohols to carbonyls.
PL-SO2Cl	Acidic Scavenger	Scavenges anilines (aromatic amines), alcohols and alkoxides. Can also be used for electrophilic activation.
PL-SO2NHNH2 Available soon	Nucleophilic Scavenger	Scavenges aldehydes and ketones.
PL-SO3H	Acid	Acid catalysis and scavenging of amines.
PL-TBD	Base	Alkylation of phenols, amines, activated methylene compounds.
PL-TEA	Base	Formation of amides, sulfonamides, carbamates.
PL-TFP	Active Ester Reagent	Activated ester formation for amide synthesis.
PL-TPP	Phosphine Reagent	Halogenation, Mitsunobu and carbon-carbon bond formation. Can also scavenge alkyl halides.

Coupling Reagents
Starting Material(s)	Product	Structure	Reaction Conditions
RCO2H + R1NH2	RCONHR1	PL-DCC Cyclohexylcarbodiimide Amide Synthesis	2 eq. PL-DCC, 1.5 eq. acid, 1.0 eq. amine in DCM, 12-16 h, 25ºC
RCO2H + R1NH2	RCONHR1	PL-EDC 1-ethyl-3-(3 dimethylamino propyl)-carbodiimide Amide Synthesis	2 eq. PL-EDC, 1.5 eq. acid, 1.0 eq. amine in DCM, 12-16 h, 25ºC
PL-TFP + RCO2H →[PL-CO2R] + R1NH2	RCONHR1	PL-TFP Tetrafluorophenol Activated Ester Formation	1.5 eq. PL-TFP 1 eq. acid, 4.5 eq. of DIC 0.6 eq. of DMAP in 4:1 DCM/DMF 2 h, 25ºC
PL-HOBt + RCO2H →[PL-CO2R] + R1NH2	RCONHR1	PL-HOBt 1-Hydroxybenzo triazole-6- carboxamidomethyl Activated ester formation Protecting group transfer (Fmoc, Cbz, Boc)	1.5 eq. PL-HOBt 1 eq. acid, 4.5 eq. of DIC 0.6 eq. of DMAP in 4:1 DCM/DMF 2 h, 25ºC

Oxidizing Reagents
Starting Material(s)	Product	Structure	Reaction Conditions
RCH2OH R1CH(OH)R2	RCHO R1COR2	PL-RuO4 MP Perruthenate Alcohols to carbonyls	0.2 eq. PL-RuO4 MP relative to alcohol. Use air as co-oxidant. 24-48 h 80ºC
R1CH(OH)CH(OH)R2 RSR1	R1CHO + R2CHO R(S=O)R1	PL-IO4 MP Periodate Alcohols to carbonyls	2 eq. PL-IO4 MP relative to 1,2 -diol or sulfide. 1,2-diol (2 h, 25ºC) sulfide (24 h, 25ºC)

Reducing Reagents
Starting Material(s)	Product	Structure	Reaction Conditions
RCHO RCOR1 RCOCl	RCH2OH RCH(OH)R1 RCH2OH	PL-BH4 MP Borohydride Carbonyl Reduction	0.5mmol PL-BH4 MP, 1.0 mmol carbonyl in EtOH/MeOH, 2-12 h, 25ºC
RCH=NR1 RCHO RCHO + R1NH2	RCH2NHR1 RCH2OH RCH2NHR1	PL-BH3(CN) MP Cyanoborohydride Reductive Amination	2.5 eq. PL-BH3(CN) MP, 1.0 eq. carbonyl in EtOH/MeOH, 1.0 eq. AcOH 1.2 eq. amine (excess can be scavenged with PL-CHO) 12-16 h, 25ºC

Neutralizing Reagents
Recommended Use	Structure	Reaction Conditions
A polymer supported carbonate equivalent, which can be used for neutralization and for the quenching of reactions across the whole spectrum of organic chemistry.	PL-CO3 MP Carbonate Basic Quenching Neutralize Ammonium Salts	3.5 eq. PL-CO3 MP, 0.5-2 h, 25ºC
A polymer supported hydrogen carbonate equivalent, which can be used for neutralization and for the quenching of reactions across the whole spectrum of organic chemistry.	PL-HCO3 MP Bicarbonate Basic Quenching Neutralize Ammonium Salts	4 eq. PL- HCO3 MP, 0.5-2 h, 25ºC

Strong Bases
Recommended Use	Structure	Reaction Conditions
Alkylation of phenols, amines, activated methylene compounds. pKa (conjugate acid) PL- TBD 〜14	PL-TBD 1,5,7-triazabicyclo[4.4.0]dec-5- ene Strong Base	2-3 eq. PL-TBD relative to limiting reagent.
Polymer supported tertiary amine base equivalents which can be used in the formation of amides, sulfonamides, carbamates, esters and sulfonates. pKa (conjugate acid) PL-TEA 〜11 pKa (conjugate acid) PL-DIPAM 〜12	PL-TEA Triethylamine Tertiary Amine Base	2-3 eq. PL-TEA or PL-DIPAM relative to limiting reagent.
	PL-DIPAM Diisoproylamine (DIEA)/Hunig’s Base Strong Tertiary Amine Base

Strong Acids
Starting Material(s)	Product	Structure	Reaction Conditions
H+	HA	PL-SO3H MP Sulfonic Acid Acid Quenching	Molar equivalents dependent on reaction type. Consult literature for specific conditions.

Electrophilic Activation
Starting Material(s)	Product	Structure	Reaction Conditions
ROH RCO2H	RX RCOCl	PL-TPP Triphenylphosphine Halogenation	1.0 eq. PL-TPP 0.5 eq. of acid or alcohol in CCl4, (X = Cl), 2 h, 80ºC for other halogens 1.0 eq. PL-TPP 0.5 eq. of alcohol in solution in CBr4/DCM (X= Br), I2/DCM (X = I).
ROH + R1R2NH	RNR1R2	PL-SO2Cl Sulfonyl chloride Alcohol activation	0.7-3.0 eq. alcohol, 5-10 h, 20ºC

Nucleophilic Activation
Starting Material(s)	Product	Structure	Reaction Conditions
R-OH + R-OH R-OH + R-NH2 R-X + R1-Y	R-O-R R-NH-R R-R1	PL-TPP Triphenylphosphine Mitsunobu reaction Carbon-Carbon Bond Formation (Wittig, Heck, Suzuki-Miyaura, Sonogashira, Stille, Negishi, Hartwig-Buchwald, Kumada-Corriu and Hiyama).	Mitsunobu 1.0 eq. alcohol, 1.0 eq. phenol, 2 eq PL-TPP 1.0 eq. DIAD, 16 h, 25ºC Wittig 2 eq. ylide resin, 8 eq. NaHMDS/THF, 1 eq. carbonyl, 16 h, 25ºC Pd coupling reactions 2 eq. of PL-TPP in place of solution phase phosphine ligand. NB. Any excess palladium, tin and boron species present in these coupling reactions can be scavenged with PL-DEAM resin.
RCOR1	RC=N-NHSO2-R1	PL-SO2NHNH2 Sulfonyl Hydrazide Sulfonyl Hydrazone Formation	3 eq. PL-SO2NHNH2 relative to carbonyl, 1-3 h 20ºC

Catalysts
Recommended Use	Structure	Reaction Conditions
A polymer supported acid equivalent, which can be used in a variety of organic reactions where protic catalysis is advantageous.	PL-SO3H Sulfonic acid Acid equivalent	Molar equivalents dependent on reaction type. Consult literature for specific reaction.

Scavengers for Electrophiles
Compounds to be Scavenged		Structure	Reaction Conditions
Acid Chlorides Sulfonyl Chlorides Isocyanates Isothiocyanates	RCOCl RSO2Cl RNCO RNCS	PL-EDA Ethylenediamine	3-6 eq. PL-EDA or PL-DETA relative to electrophile, 4 h, 20ºC
		PL-DETA Diethylenetriamine
PL-BZA resin can be used in the formation of traceless triazine linkers via reaction with aryl diazonium species.		PL-BZA Benzylamine	Consult literature for specific reaction.
A polymer supported piperidine equivalent, which can be used as a scavenger for electrophiles, It can also be used as a catalyst for Knoevenagel reactions and in Fmoc protecting group removal.		PL-PPZ Piperazine	2-3eq. PL-PPZ.
Boronic Acids Palladium, Tin, Titanium and other Lewis Acids	RB(OH)2 Ti(IV), Sn(IV) Pd	PL-DEAM Diethanolamine	2-3 eq. PL-DEAM relative to boronic acid. 4 h, 20ºC Metal scavenging 12-24 h 20ºC
Alkylating Agents	RX RSO3R1 mesylates, tosylates	PL-TPP Triphenylphosphine	3 eq. PL-TPP, 16 h, 20ºC
Carbonyls	RCHO, RCOR1	PL-SO2NHNH2 Sulfonyl Hydrazide	3 eq. PL-SO2NHNH2 relative to carbonyl, 1-3 h 20ºC

Scavengers for Nucleophiles
Compounds to be Scavenged		Structure	Reaction Conditions
Primary & Secondary Amines Hydrazines Thiols Thiolates	RNH2, RR1NH RNHNH2 RSH RS-	PL-NCO Isocyanate	2-3 eq. PL-NCO relative to nucleophile, 1-16 h, 20ºC
Primary & Secondary Amines Hydrazines Thiols Thiolates	RNH2, RR1NH RNHNH2 RSH RS-	PL-MIA Methylisatoic anhydride	2-3 eq. PL-MIA relative to nucleophile, 3-18 h, 20ºC
Selective to Primary Amines Enolates	RNH2, RCOCH=CO-R1	PL-CHO Benzaldehyde	2-3 eq. PL-CHO relative to nucleophile, glacial AcOH (trace), 4-18 h, 50ºC
Selective to Primary Amines Enolates	RNH2, RCOCH=CO-R1	PL-AAEM Acetoacetoxyethyl ketoester	2-3 eq. PL-AAEM relative to nucleophile, 3-18 h, 20ºC
Anilines (Aromatics) Alcohols Alkoxides	ArNH2 ROH	PL-SO2Cl Sulfonyl Chloride	2-3 eq. PL-SO2Cl relative to nucleophile, 1-16 h, 20ºC

Basic Scavengers
Compounds to be Scavenged	Structure	Reaction Conditions
Used in the scavenging of acids H-X	PL-PIP Piperidine	3 eq. PL-PIP, PL-MPH or PL-MPPZ relative to acid.
	PL-MPH Morpholine
	PL-MPPZ N-methylpiperazine

Acidic Scavengers
Compounds to be Scavenged		Structure	Reaction Conditions
Acids, Acidic Phenols Activated ester reagents	H+ Ar-OH HOBt, HOSu , HONB,	PL-CO3 MP Carbonate	3 eq. PL-CO3 MP or PL-HCO3 MP relative to acid.
		PL-HCO3 MP Bicarbonate
Tertiary Amines	NR3	PL-SO3H Sulfonic Acid	2-3 eq. PL-SO3H relative to tertiary amine.
Alkoxides	R-O-	PL-SO2Cl Sulfonyl Chloride	2-3 eq. PL-SO2Cl relative to alkoxide.